the nature of persistent conformational chirality ... · supportinginformation s1* supporting...

Supporting Information S1

Supporting Information

The Nature of Persistent Conformational

Chirality, Racemization Mechanisms, and

Predictions in Diarylether Heptanoid

Cyclophane Natural Products

Ommidala Pattawong, Nicholas T. Rosson, M. Quamar

Salih, Christopher M. Beaudry* and Paul Ha-Yeon Cheong*

Department of Chemistry, Oregon State University,

153 Gilbert Hall, Corvallis, Oregon, 97331-4003.

E-mail: [email protected], [email protected]

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2014


1 Table of Content

2 Full Authorship of Gaussian ......................................................................................................... 8 3 Additional Figures ............................................................................................................................ 9

3.1 Isomers of Garugamblin I ........................................................................................................................... 9 3.2 Minimum Energy Pathway for Stereoisomerization of C9-Z-Garugamblin I .............................. 10

4 Table of Solvation Corrections and MP2 Limit Energies ................................................ 11 4.1 Acerogenin L ............................................................................................................................................... 11 4.2 Galeon ........................................................................................................................................................... 12 4.3 Tautomers of 9’-Desmethylgarugamblin I ........................................................................................... 14 4.4 Model Systems for Classical and Non-classical Hydrogen Bonding .......................................... 15 4.5 C9-Z-9’-Desmethylgarugamblin I ........................................................................................................... 16 4.6 C9-E-9’-Desmethylgarugamblin I ........................................................................................................... 17 4.7 C9-E-Garugamblin I ................................................................................................................................... 18 4.8 C11-E-Garugamblin I .................................................................................................................................. 19

5 Coordinates, Energies, and Thermal Corrections of All Structures Reported in the Manuscript and listed by the Reactions ....................................................................................... 20

5.1 Acerogenin L ............................................................................................................................................... 20 5.1.1 Acerogenin L ......................................................................................................................................................... 20 5.1.2 TSa .............................................................................................................................................................................. 20 5.1.3 TSb .............................................................................................................................................................................. 20 5.1.4 TSc .............................................................................................................................................................................. 21 5.1.5 Inta ............................................................................................................................................................................... 21 5.1.6 Intb ............................................................................................................................................................................... 22 5.1.7 Intc ............................................................................................................................................................................... 22 5.1.8 TSa→ab ........................................................................................................................................................................ 23 5.1.9 TSa→ac ........................................................................................................................................................................ 23 5.1.10 TSb→ba ..................................................................................................................................................................... 24 5.1.11 TSb→bc ..................................................................................................................................................................... 24 5.1.12 TSc→ca ..................................................................................................................................................................... 25 5.1.13 TSc→cb ..................................................................................................................................................................... 25 5.1.14 Intab ........................................................................................................................................................................... 26 5.1.15 Intac ........................................................................................................................................................................... 26 5.1.16 Intba ........................................................................................................................................................................... 26 5.1.17 Intbc ........................................................................................................................................................................... 27 5.1.18 Intca ........................................................................................................................................................................... 27 5.1.19 Intcb ........................................................................................................................................................................... 28 5.1.20 TSab→abc .................................................................................................................................................................. 28 5.1.21 TSac→acb .................................................................................................................................................................. 29 5.1.22 TSba→bac .................................................................................................................................................................. 29 5.1.23 TSbc→bca .................................................................................................................................................................. 30 5.1.24 TSca→cab .................................................................................................................................................................. 30 5.1.25 TScb→cba .................................................................................................................................................................. 31 5.1.26 ent-Acerogenin L .............................................................................................................................................. 31

5.2 Galeon ........................................................................................................................................................... 31 5.2.1 Galeon ...................................................................................................................................................................... 31 5.2.2 TSa .............................................................................................................................................................................. 32


5.2.3 TSb .............................................................................................................................................................................. 32 5.2.4 TSc .............................................................................................................................................................................. 33 5.2.5 TSd .............................................................................................................................................................................. 33 5.2.6 Inta ............................................................................................................................................................................... 34 5.2.7 Intb ............................................................................................................................................................................... 34 5.2.8 Intc ............................................................................................................................................................................... 35 5.2.9 Intd ............................................................................................................................................................................... 35 5.2.10 TSa→ab ..................................................................................................................................................................... 36 5.2.11 TSa→ac ..................................................................................................................................................................... 36 5.2.12 TSa→ad ..................................................................................................................................................................... 37 5.2.13 TSb→ba ..................................................................................................................................................................... 37 5.2.14 TSb→bc ..................................................................................................................................................................... 38 5.2.15 TSb→bd ..................................................................................................................................................................... 38 5.2.16 TSc→ca ..................................................................................................................................................................... 39 5.2.17 TSc→cb ..................................................................................................................................................................... 39 5.2.18 TSc→cd ..................................................................................................................................................................... 40 5.2.19 TSd→da ..................................................................................................................................................................... 40 5.2.20 TSd→db ..................................................................................................................................................................... 41 5.2.21 TSd→dc ..................................................................................................................................................................... 41 5.2.22 Intab ........................................................................................................................................................................... 42 5.2.23 Intac ........................................................................................................................................................................... 42 5.2.24 Intad ........................................................................................................................................................................... 42 5.2.25 Intba ........................................................................................................................................................................... 43 5.2.26 Intbc ........................................................................................................................................................................... 43 5.2.27 Intbd ........................................................................................................................................................................... 44 5.2.28 Intca ........................................................................................................................................................................... 44 5.2.29 Intcb ........................................................................................................................................................................... 45 5.2.30 Intcd ........................................................................................................................................................................... 45 5.2.31 Intda ........................................................................................................................................................................... 46 5.2.32 Intdb ........................................................................................................................................................................... 46 5.2.33 Intdc ........................................................................................................................................................................... 47 5.2.34 TSab→abc .................................................................................................................................................................. 47 5.2.35 TSab→abd ................................................................................................................................................................. 48 5.2.36 TSac→acb .................................................................................................................................................................. 48 5.2.37 TSac→acd .................................................................................................................................................................. 49 5.2.38 TSad→adb ................................................................................................................................................................. 49 5.2.39 TSad→adc .................................................................................................................................................................. 50 5.2.40 TSba→bac .................................................................................................................................................................. 50 5.2.41 TSba→bad ................................................................................................................................................................. 51 5.2.42 TSbc→bca .................................................................................................................................................................. 51 5.2.43 TSbc→bcd .................................................................................................................................................................. 52 5.2.44 TSbd→bda ................................................................................................................................................................. 52 5.2.45 TSbd→bdc .................................................................................................................................................................. 53 5.2.46 TSca→cab .................................................................................................................................................................. 53 5.2.47 TSca→cad .................................................................................................................................................................. 53 5.2.48 TScb→cba .................................................................................................................................................................. 54 5.2.49 TScb→cbd .................................................................................................................................................................. 54 5.2.50 TScd→cda .................................................................................................................................................................. 54 5.2.51 TScd→cdb .................................................................................................................................................................. 55 5.2.52 TSda→dab ................................................................................................................................................................. 55


5.2.53 TSda→dac .................................................................................................................................................................. 56 5.2.54 TSdb→dba ................................................................................................................................................................. 56 5.2.55 TSdb→dbc .................................................................................................................................................................. 57 5.2.56 TSdc→dca .................................................................................................................................................................. 57 5.2.57 TSdc→dcb .................................................................................................................................................................. 58 5.2.58 TSd→dc ..................................................................................................................................................................... 58 5.2.59 Intabc ......................................................................................................................................................................... 59 5.2.60 Intabd ......................................................................................................................................................................... 59 5.2.61 Intacb ......................................................................................................................................................................... 60 5.2.62 Intacd ......................................................................................................................................................................... 60 5.2.63 Intadb ......................................................................................................................................................................... 61 5.2.64 Intadc ......................................................................................................................................................................... 61 5.2.65 Intbac ......................................................................................................................................................................... 62 5.2.66 Intbad ......................................................................................................................................................................... 62 5.2.67 Intbca ......................................................................................................................................................................... 63 5.2.68 Intbcd ......................................................................................................................................................................... 63 5.2.69 Intbda ......................................................................................................................................................................... 64 5.2.70 Intbdc ......................................................................................................................................................................... 64 5.2.71 Intcab ......................................................................................................................................................................... 65 5.2.72 Intcad ......................................................................................................................................................................... 65 5.2.73 Intcba ......................................................................................................................................................................... 65 5.2.74 Intcbd ......................................................................................................................................................................... 66 5.2.75 Intcda ......................................................................................................................................................................... 66 5.2.76 Intcdb ......................................................................................................................................................................... 67 5.2.77 Intdab ......................................................................................................................................................................... 67 5.2.78 Intdac ......................................................................................................................................................................... 68 5.2.79 Intdba ......................................................................................................................................................................... 68 5.2.80 Intdbc ......................................................................................................................................................................... 69 5.2.81 Intdca ......................................................................................................................................................................... 69 5.2.82 Intdcb ......................................................................................................................................................................... 70 5.2.83 TSabc→abcd .............................................................................................................................................................. 70 5.2.84 TSabd→abdc .............................................................................................................................................................. 71 5.2.85 TSacb→acbd .............................................................................................................................................................. 71 5.2.86 TSacd→acdb .............................................................................................................................................................. 72 5.2.87 TSadb→adbc .............................................................................................................................................................. 72 5.2.88 TSadc→adcb .............................................................................................................................................................. 73 5.2.89 TSbac→bacd .............................................................................................................................................................. 73 5.2.90 TSbad→badc .............................................................................................................................................................. 74 5.2.91 TSbca→bcad .............................................................................................................................................................. 74 5.2.92 TSbcd→bcda .............................................................................................................................................................. 75 5.2.93 TSbda→bdac .............................................................................................................................................................. 75 5.2.94 TSbdc→bdca .............................................................................................................................................................. 76 5.2.95 TScab→cabd .............................................................................................................................................................. 76 5.2.96 TScad→cadb .............................................................................................................................................................. 76 5.2.97 TScba→cbad .............................................................................................................................................................. 77 5.2.98 TScbd→cbda .............................................................................................................................................................. 77 5.2.99 TScda→cdab .............................................................................................................................................................. 78 5.2.100 TScdb→cdba ............................................................................................................................................................ 78 5.2.101 TSdab→dabc ........................................................................................................................................................... 79 5.2.102 TSdac→dacb ............................................................................................................................................................ 79


5.2.103 TSdba→dbac ........................................................................................................................................................... 80 5.2.104 TSdbc→dbca ............................................................................................................................................................ 80 5.2.105 TSdca→dcab ............................................................................................................................................................ 81 5.2.106 TSdcb→dcba ............................................................................................................................................................ 81 5.2.107 ent-Galeon ......................................................................................................................................................... 82

5.3 Tautomers of 9’-Desmethylgarugamblin I ........................................................................................... 82 5.3.1 C9-E-Tautomer ..................................................................................................................................................... 82 5.3.2 C9-Z-Tautomer ...................................................................................................................................................... 83 5.3.3 C11-E-Tautomer .................................................................................................................................................... 83 5.3.4 C11-Z-Tautomer .................................................................................................................................................... 84 5.3.5 Keto-tautomer ....................................................................................................................................................... 84

5.4 Model Systems for Classical and Non-classical Hydrogen Bonding .......................................... 85 5.4.1 Dimethoxybenzene-Enol complex ............................................................................................................. 85 5.4.2 Dimethoxybenzene-Ketone complex ........................................................................................................ 85 5.4.3 Dimethoxybenzene ............................................................................................................................................ 85 5.4.4 E-vinyligous Ester ............................................................................................................................................... 86 5.4.5 E-vinyligous Ester Rotation TS .................................................................................................................... 86 5.4.6 E-vinyligous Ester-2 ........................................................................................................................................... 86 5.4.7 Monomethoxybenzene-Enol complex ...................................................................................................... 87 5.4.8 Monomethoxybenzene-Ketone complex ................................................................................................ 87 5.4.9 Monomethoxybenzene ..................................................................................................................................... 88 5.4.10 Z-vinyligous Ester ............................................................................................................................................. 88 5.4.11 Z-vinyligous Ester ............................................................................................................................................. 88 5.4.12 Z-vinyligous Ester Rotation TS .................................................................................................................. 89 5.4.13 Enol .......................................................................................................................................................................... 89 5.4.14 Ketone .................................................................................................................................................................... 89

5.5 C9-Z-9’-Desmethylgarugamblin I ........................................................................................................... 89 5.5.1 C9-Z-9’-Desmethylgarugamblin I ................................................................................................................. 89 5.5.2 TSa .............................................................................................................................................................................. 90 5.5.3 TSbc ............................................................................................................................................................................. 90 5.5.4 TSc .............................................................................................................................................................................. 91 5.5.5 Inta ............................................................................................................................................................................... 91 5.5.6 Intc ............................................................................................................................................................................... 92 5.5.7 TSa→ab ........................................................................................................................................................................ 92 5.5.8 TSa→ac ........................................................................................................................................................................ 93 5.5.9 TSc→ca ........................................................................................................................................................................ 93 5.5.10 TSc→cb ..................................................................................................................................................................... 94 5.5.11 Intab ........................................................................................................................................................................... 94 5.5.12 Intac ........................................................................................................................................................................... 95 5.5.13 Intbc ........................................................................................................................................................................... 95 5.5.14 Intca ........................................................................................................................................................................... 96 5.5.15 Intcb ........................................................................................................................................................................... 96 5.5.16 TSab→abc .................................................................................................................................................................. 96 5.5.17 TSac→acb .................................................................................................................................................................. 97 5.5.18 TSbc→bca .................................................................................................................................................................. 97 5.5.19 TSca→cab .................................................................................................................................................................. 98 5.5.20 TScb→cba .................................................................................................................................................................. 98 5.5.21 ent- C9-Z-9’-Desmethylgarugamblin I ................................................................................................... 99

5.6 C9-E-9’-Desmethylgarugamblin I ........................................................................................................... 99 5.6.1 C9-E-9’-Desmethylgarugamblin I ................................................................................................................ 99


5.6.2 TSa ........................................................................................................................................................................... 100 5.6.3 TSb ........................................................................................................................................................................... 100 5.6.4 TSc ........................................................................................................................................................................... 101 5.6.5 Inta ............................................................................................................................................................................ 101 5.6.6 Intb ............................................................................................................................................................................ 102 5.6.7 Intc ............................................................................................................................................................................ 102 5.6.8 TSa→ab ..................................................................................................................................................................... 103 5.6.9 TSa→acb ................................................................................................................................................................... 103 5.6.10 TSb→ba .................................................................................................................................................................. 104 5.6.11 TSb→bc .................................................................................................................................................................. 104 5.6.12 TSc→ca .................................................................................................................................................................. 105 5.6.13 TSc→cb .................................................................................................................................................................. 105 5.6.14 Intab ........................................................................................................................................................................ 106 5.6.15 Intca ........................................................................................................................................................................ 106 5.6.16 TSca→cab ............................................................................................................................................................... 106 5.6.17 ent- C9-E-9’-Desmethylgarugamblin I ................................................................................................. 107

5.7 C9-E-Garugamblin I ................................................................................................................................. 107 5.7.1 C9-E-Garugamblin I ......................................................................................................................................... 107 5.7.2 TSa ........................................................................................................................................................................... 108 5.7.3 TSb ........................................................................................................................................................................... 108 5.7.4 TSc ........................................................................................................................................................................... 109 5.7.5 Inta ............................................................................................................................................................................ 109 5.7.6 Intb ............................................................................................................................................................................ 110 5.7.7 Intc ............................................................................................................................................................................ 110 5.7.8 TSa→ab ..................................................................................................................................................................... 111 5.7.9 TSa→acb ................................................................................................................................................................... 111 5.7.10 TSb→ba .................................................................................................................................................................. 112 5.7.11 TSb→bca ................................................................................................................................................................ 112 5.7.12 TSc→ca .................................................................................................................................................................. 113 5.7.13 TSc→cb .................................................................................................................................................................. 113 5.7.14 Intab ........................................................................................................................................................................ 114 5.7.15 Intba ........................................................................................................................................................................ 114 5.7.16 Intca ........................................................................................................................................................................ 115 5.7.17 Intcb ........................................................................................................................................................................ 115 5.7.18 TSab→abc ............................................................................................................................................................... 116 5.7.19 TSba→bac ............................................................................................................................................................... 116 5.7.20 TSca→cab ............................................................................................................................................................... 117 5.7.21 TScb→cba ............................................................................................................................................................... 117 5.7.22 ent- C9-E-Garugamblin I ............................................................................................................................ 118

5.8 C11-E-Garugamblin I ................................................................................................................................ 118 5.8.1 C11-E-Garugamblin I ....................................................................................................................................... 118 5.8.2 TSa ........................................................................................................................................................................... 119 5.8.3 TSb ........................................................................................................................................................................... 119 5.8.4 TSc ........................................................................................................................................................................... 120 5.8.5 Inta ............................................................................................................................................................................ 120 5.8.6 Intb ............................................................................................................................................................................ 121 5.8.7 Intc ............................................................................................................................................................................ 121 5.8.8 TSa→abc ................................................................................................................................................................... 122 5.8.9 TSa→ac ..................................................................................................................................................................... 122 5.8.10 TSb→ba .................................................................................................................................................................. 123


5.8.11 TSb→bc .................................................................................................................................................................. 123 5.8.12 TSc→ca .................................................................................................................................................................. 124 5.8.13 TSc→cb .................................................................................................................................................................. 124 5.8.14 Intac ........................................................................................................................................................................ 125 5.8.15 Intba ........................................................................................................................................................................ 125 5.8.16 Intbc ........................................................................................................................................................................ 126 5.8.17 Intca ........................................................................................................................................................................ 126 5.8.18 Intcb ........................................................................................................................................................................ 127 5.8.19 TSac→acb ............................................................................................................................................................... 127 5.8.20 TSba→bac ............................................................................................................................................................... 128 5.8.21 TSbc→bca ............................................................................................................................................................... 128 5.8.22 TSca→cab ............................................................................................................................................................... 129 5.8.23 TScb→cba ............................................................................................................................................................... 129 5.8.24 ent- C11-E-Garugamblin I ........................................................................................................................... 130


2 Full Authorship of Gaussian

Gaussian 09 - Gaussian 09, Revision A.1, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, Jr., J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, N. J.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian, Inc., Wallingford CT, 2009.


S9

S9

3 Additional Figures 3.1 Isomers of Garugamblin I

O

OMeO

MeO O

O

MeO

MeO

O

MeO

MeO

O

C11-Z-garugamblin I∆G = 6.5

C11-E-garugamblin I∆G = 1.8

C9-E-garugamblin I∆G = 0.0

C9-Z-garugamblin I∆G = 4.4

H H

H

O

MeO

MeO

O

H

2.5

There are a total of four tautomers of garugamblin I: C9-E-, C11-E-, C9-Z- and C11-Z-, where C9 and C11 describe the position of the carbonyl, and Z/E define the stereochemistry of the vinylogous ester. The Z-stereoisomers are less stable than the E by ~4–6 kcal/mol due to the vinylogous ester distortions from planarity. Similar to the 9’-desmethy analogue, C9-E/Z tautomers are more stable than C11-E/Z due to stronger CH···O interactions between H6 and C9O.


S10

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3.2 Minimum Energy Pathway for Stereoisomerization of C9-Z-Garugamblin I

The reaction coordinate diagram shows the complete stereoisomerization pathway for the C9-Z-garugamblin I. The rotation of vinylogous ester is the RDS with barrier of 13.8 kcal/mol. The steroisomerization of C9-Z tautomer is much easier than the C9-E. All energies, vibrational frequencies and thermal corrections are from SCS-MP2/def2-∞//B3LYP/6-31G* with PCM (dichlorobenzene) solvation corrections and given in kcal/mol. Green lines indicate possible electrostatic interactions and distances given in Å.


S11

S11

4 Table of Solvation Corrections and MP2 Limit Energies 4.1 Acerogenin L

Description File ∆Gsol MP2Limit Acerogenin-‐L CO-‐mAnsa-‐pAnsa-‐000-‐acerogenin-‐L.log -‐0.009723063 -‐961.0134416

TSa mAnsa-‐CO-‐pAnsa-‐005-‐Acerogenin-‐L-‐TSmAnsa.log -‐0.009235518 -‐960.9959856

TSb CO-‐mAnsa-‐pAnsa-‐005-‐acerogenin-‐L-‐TSco.log -‐0.010252527 -‐961.0031126 TSc pAnsa-‐CO-‐mAnsa-‐Acerogenin-‐L-‐d-‐TS.log -‐0.009605863 -‐961.0002501 Inta mAnsa-‐CO-‐pAnsa-‐010-‐Acerogenin-‐L.log -‐0.010399469 -‐961.0100882 Intb CO-‐mAnsa-‐pAnsa-‐010-‐acerogenin-‐L.log -‐0.009517715 -‐961.0068907 Intc pAnsa-‐CO-‐mAnsa-‐Acerogenin-‐L-‐e-‐GS.log -‐0.009323366 -‐961.0104257

TSa→ab mAnsa-‐CO-‐pAnsa-‐015-‐Acerogenin-‐L-‐TSco.log -‐0.010618442 -‐961.0047674 TSa→ac mAnsa-‐pAnsa-‐CO-‐015-‐Acerogenin-‐L-‐TSpAnas.log -‐0.009605769 -‐961.0002487

TSb→ba CO-‐mAnsa-‐pAnsa-‐015-‐acerogenin-‐L-‐TSmAnsa.log -‐0.010264156 -‐960.993642

TSb→bc CO-‐pAnsa-‐mAnsa-‐015-‐acerogenin-‐L-‐TSpAnsa.log -‐0.011379417 -‐960.9974958 TSc→cb pAnsa-‐CO-‐mAnsa-‐Acerogenin-‐L-‐f-‐TS.log -‐0.010068157 -‐961.0034231

TSc→ca pAnsa-‐mAnsa-‐CO-‐015-‐acerogenin-‐L-‐TSmAnsa.log -‐0.008668789 -‐960.9947093

Intab mAnsa-‐CO-‐pAnsa-‐020-‐Acerogenin-‐L.log -‐0.009323429 -‐961.0104218 Intac mAnsa-‐pAnsa-‐CO-‐020-‐Acerogenin-‐L.log -‐0.009323323 -‐961.0104223 Intba CO-‐mAnsa-‐pAnsa-‐020-‐acerogenin-‐L.log -‐0.009323137 -‐961.0104238 Intbc CO-‐pAnsa-‐mAnsa-‐020-‐acerogenin-‐L.log -‐0.010396649 -‐961.010092 Intca pAnsa-‐mAnsa-‐CO-‐020-‐acerogenin-‐L.log -‐0.009517203 -‐961.0068848 Intcb pAnsa-‐CO-‐mAnsa-‐Acerogenin-‐L-‐i-‐GS.log -‐0.010395964 -‐961.010093

TSab→abc mAnsa-‐CO-‐pAnsa-‐025-‐Acerogenin-‐L-‐TSpAnsa.log -‐0.008815639 -‐960.9974207 TSac→acb mAnsa-‐pAnsa-‐CO-‐025-‐Acerogenin-‐L-‐TSco.log -‐0.010068818 -‐961.0034228

TSba→bac CO-‐mAnsa-‐pAnsa-‐025-‐acerogenin-‐L-‐TS-‐pAnsa.log -‐0.009606068 -‐961.0002496

TSbc→bca CO-‐pAnsa-‐mAnsa-‐025-‐acerogenin-‐L-‐TSmAnsa.log -‐0.01103197 -‐961.0005781

TSca→cab pAnsa-‐mAnsa-‐CO-‐025-‐acerogenin-‐L-‐TSco.log -‐0.010252511 -‐961.0031148 TScb→cba pAnsa-‐CO-‐mAnsa-‐Acerogenin-‐L-‐j-‐TS.log -‐0.011031976 -‐961.0005782 ent-‐

Acerogenin-‐L CO-‐mAnsa-‐pAnsa-‐030-‐acerogenin-‐L.log -‐0.009721827 -‐961.0134378


S12

S12

4.2 Galeon

Description File ∆Gsol MP2Limit Galeon 000-‐Galeon-‐New-‐GS.log -‐0.0105355 -‐1075.469529 TSa 005-‐TS-‐C7-‐8-‐Galeon.log -‐0.01065795 -‐1075.457988 TSb 005-‐TS-‐COout-‐Galeon.log -‐0.01136841 -‐1075.458064 TSc 005-‐TS2-‐C11-‐12in-‐Galeon.log -‐0.01048313 -‐1075.456625 TSd 005-‐TS-‐Ph-‐Galeon.log -‐0.01173573 -‐1075.39806 Inta 010-‐GS-‐C7-‐8-‐Galeon.log -‐0.01009082 -‐1075.467855 Intb 010-‐GS-‐COout-‐Galeon.log -‐0.01147141 -‐1075.458534 Intc 010-‐GS-‐C11-‐12in-‐Galeon.log -‐0.01091599 -‐1075.464893 Intd 010-‐GS-‐Ph-‐Galeon.log -‐0.01115891 -‐1075.467773

TSa→ab 015-‐TS2-‐C7-‐8-‐COin-‐Galeon.log -‐0.0115255 -‐1075.458159 TSa→ac 015-‐TS2-‐C7-‐8-‐11-‐12in-‐Galeon.log -‐0.01011161 -‐1075.451214 TSa→ad 015-‐TS-‐C7-‐8-‐Ph-‐Galeon.log -‐0.01249372 -‐1075.368406 TSb→ba 015-‐TS-‐COout-‐C7-‐8-‐Galeon.log -‐0.01349116 -‐1075.444988 TSb→bc 015-‐TS-‐COout-‐C11-‐12out-‐Galeon.log -‐0.0135275 -‐1075.437962 TSb→bd 015-‐TS-‐COout-‐Ph-‐Galeon.log -‐0.0131108 -‐1075.37595 TSc→ca 015-‐TS-‐C11-‐12out-‐7-‐8-‐Galeon.log -‐0.01023531 -‐1075.450705 TSc→cb 015-‐TS2-‐C11-‐12in-‐Coin-‐Galeon.log -‐0.01293891 -‐1075.45731 TSc→cd 015-‐TS-‐C11-‐12in-‐Ph-‐Galeon.log -‐0.01165467 -‐1075.390281 TSd→da 015-‐TS-‐Ph-‐C7-‐8in-‐Galeon.log -‐0.01038518 -‐1075.45091 TSd→db 015-‐TS-‐Ph-‐COin-‐Galeon.log -‐0.01160702 -‐1075.45756 TSd→dc 015-‐TS2-‐Ph-‐C11-‐12-‐Galeon.log -‐0.01109248 -‐1075.454263 Intab 020-‐GS2-‐C7-‐8-‐COin-‐Galeon.log -‐0.01110206 -‐1075.463674 Intac 020-‐GS-‐C7-‐8-‐11-‐12in-‐Galeon.log -‐0.00949259 -‐1075.46446 Intad 020-‐GS-‐C7-‐8-‐Ph-‐Galeon.log -‐0.01302215 -‐1075.461853 Intba 020-‐GS-‐COout-‐C7-‐8-‐Galeon.log -‐0.01099894 -‐1075.465122 Intbc 020-‐GS-‐COout-‐C11-‐12out-‐Galeon.log -‐0.01302339 -‐1075.461855 Intbd 020-‐GS-‐COout-‐Ph-‐Galeon.log -‐0.00956784 -‐1075.464831 Intca 020-‐GS-‐C11-‐12in-‐7-‐8-‐Galeon.log -‐0.00949506 -‐1075.464455 Intcb 020-‐GS2-‐C11-‐12in-‐Coin-‐Galeon.log -‐0.01302259 -‐1075.461855 Intcd 020-‐GS-‐C11-‐12in-‐Ph-‐Galeon.log -‐0.01110192 -‐1075.463673 Intda 020-‐GS-‐Ph-‐C7-‐8in-‐Galeon.log -‐0.01302288 -‐1075.461848 Intdb 020-‐GS-‐Ph-‐COin-‐Galeon.log -‐0.00949359 -‐1075.464457 Intdc 020-‐GS-‐Ph-‐C11-‐12-‐Galeon.log -‐0.01110291 -‐1075.463674

TSab→abc 025-‐TS-‐C7-‐8-‐COin-‐C11-‐12out-‐Galeon.log -‐0.01218854 -‐1075.446245 TSab→abd 025-‐TS-‐C7-‐8-‐COout-‐Ph-‐Galeon.log -‐0.01268581 -‐1075.388585 TSac→acb 025-‐TS-‐C7-‐8-‐11-‐12in-‐COin-‐Galeon.log -‐0.01160673 -‐1075.45756 TSac→acd 025-‐TS-‐C7-‐8-‐11-‐12in-‐Ph-‐Galeon.log -‐0.01193958 -‐1075.371053 TSad→adb 025-‐TS1-‐C7-‐8-‐Ph-‐COin-‐Galeon.log -‐0.01293893 -‐1075.45731 TSad→adc 025-‐TS2-‐C7-‐8-‐Ph-‐C11-‐12in-‐Galeon.log -‐0.01239011 -‐1075.44661


S13

S13

TSba→bac 025-‐TS1-‐COin-‐C7-‐8out-‐11-‐12out-‐Galeon.log -‐0.01167055 -‐1075.457031 TSba→bad 025-‐TS-‐COin-‐C7-‐8out-‐Ph-‐Galeon.log -‐0.01268587 -‐1075.388583 TSbc→bca 025-‐TS-‐COout-‐C11-‐12out-‐7-‐8-‐Galeon.log -‐0.01371299 -‐1075.451801 TSbc→bcd 025-‐TS-‐COout-‐C11-‐12out-‐Ph-‐Galeon.log -‐0.01317108 -‐1075.386645 TSbd→bda 025-‐TS-‐COin-‐Ph-‐C7-‐8-‐Galeon.log -‐0.01071025 -‐1075.450791 TSbd→bdc 025-‐TS-‐COout-‐Ph-‐C11-‐12in-‐Galeon.log -‐0.01190903 -‐1075.44132 TSca→cab 025-‐TS-‐C11-‐12in-‐7-‐8-‐COin-‐Galeon.log -‐0.0116067 -‐1075.457559 TSca→cad 025-‐TS-‐C11-‐12in-‐7-‐8-‐Ph-‐Galeon.log -‐0.01193887 -‐1075.371054 TScb→cba 025-‐TS-‐C11-‐12in-‐Coin-‐C7-‐8-‐Galeon.log -‐0.01371298 -‐1075.451801 TScb→cbd 025-‐TS-‐C11-‐12in-‐Coin-‐Ph-‐Galeon.log -‐0.01317113 -‐1075.386644 TScd→cda 025-‐TS-‐C11-‐12out-‐Ph-‐C7-‐8-‐Galeon.log -‐0.0099556 -‐1075.449535 TScd→cdb 025-‐TS2-‐C11-‐12out-‐Ph-‐COin-‐Galeon.log -‐0.01188895 -‐1075.459271 TSda→dab 025-‐TS3-‐Ph-‐C7-‐8in-‐COin-‐Galeon.log -‐0.01130532 -‐1075.458996 TSda→dac 025-‐TS2-‐Ph-‐C7-‐8in-‐11-‐12in-‐Galeon.log -‐0.01239188 -‐1075.44661 TSdb→dba 025-‐TS-‐Ph-‐COin-‐C7-‐8-‐Galeon.log -‐0.01023487 -‐1075.450705 TSdb→dbc 025-‐TS-‐Ph-‐COout-‐C11-‐12out-‐Galeon.log -‐0.01190882 -‐1075.441321 TSdc→dca 025-‐TS-‐Ph-‐C11-‐12in-‐7-‐8out-‐Galeon.log -‐0.00995596 -‐1075.449537 TSdc→dcb 025-‐TS1-‐Ph-‐C11-‐12-‐COin-‐Galeon.log -‐0.01152468 -‐1075.458159 Intabc 030-‐GS-‐C7-‐8-‐COin-‐C11-‐12out-‐Galeon.log -‐0.01115767 -‐1075.467773 Intabd 030-‐GS-‐C7-‐8-‐COout-‐Ph-‐Galeon.log -‐0.01073165 -‐1075.465852 Intacb 030-‐GS-‐C7-‐8-‐11-‐12in-‐COin-‐Galeon.log -‐0.01115889 -‐1075.467771 Intacd 030-‐GS-‐C7-‐8-‐11-‐12in-‐Ph-‐Galeon.log -‐0.01204711 -‐1075.458502 Intadb 030-‐GS2-‐C7-‐8-‐Ph-‐COin-‐Galeon.log -‐0.01203368 -‐1075.462023 Intadc 030-‐GS-‐C7-‐8-‐Ph-‐C11-‐12in-‐Galeon.log -‐0.01204686 -‐1075.458499 Intbac 030-‐GS2-‐COin-‐C7-‐8out-‐11-‐12out-‐Galeon.log -‐0.01115739 -‐1075.467773 Intbad 030-‐GS-‐COin-‐C7-‐8out-‐Ph-‐Galeon.log -‐0.0107331 -‐1075.465853 Intbca 030-‐GS-‐COout-‐C11-‐12out-‐7-‐8-‐Galeon.log -‐0.01115773 -‐1075.467774 Intbcd 030-‐GS-‐COout-‐C11-‐12out-‐Ph-‐Galeon.log -‐0.01009173 -‐1075.467855 Intbda 030-‐GS-‐COin-‐Ph-‐C7-‐8-‐Galeon.log -‐0.0107351 -‐1075.465857 Intbdc 030-‐GS-‐COout-‐Ph-‐C11-‐12in-‐Galeon.log -‐0.01009173 -‐1075.467855 Intcab 030-‐GS-‐C11-‐12in-‐7-‐8-‐COin-‐Galeon.log -‐0.01115879 -‐1075.467772 Intcad 030-‐GS-‐C11-‐12in-‐7-‐8-‐Ph-‐Galeon.log -‐0.01204733 -‐1075.458499 Intcba 030-‐GS-‐C11-‐12in-‐Coin-‐C7-‐8-‐Galeon.log -‐0.0111576 -‐1075.467773 Intcbd 030-‐GS-‐C11-‐12in-‐Coin-‐Ph-‐Galeon.log -‐0.01009151 -‐1075.467854 Intcda 030-‐GS-‐C11-‐12out-‐Ph-‐C7-‐8-‐Galeon.log -‐0.01147107 -‐1075.458534 Intcdb 030-‐GS2-‐C11-‐12out-‐Ph-‐COin-‐Galeon.log -‐0.01009217 -‐1075.467852 Intdab 030-‐GS3-‐Ph-‐C7-‐8in-‐COin-‐Galeon.log -‐0.01091287 -‐1075.464895 Intdac 030-‐GS-‐Ph-‐C7-‐8in-‐11-‐12in-‐Galeon.log -‐0.01204738 -‐1075.458485 Intdba 030-‐GS-‐Ph-‐COin-‐C7-‐8-‐Galeon.log -‐0.01091382 -‐1075.464893 Intdbc 030-‐GS-‐Ph-‐COout-‐C11-‐12out-‐Galeon.log -‐0.01009032 -‐1075.467858 Intdca 030-‐GS-‐Ph-‐C11-‐12in-‐7-‐8out-‐Galeon.log -‐0.01146742 -‐1075.458532 Intdcb 030-‐GS2-‐Ph-‐C11-‐12-‐COin-‐Galeon.log -‐0.01009193 -‐1075.467852

Tsabc→abcd 035-‐TS-‐C7-‐8-‐COin-‐C11-‐12out-‐Ph-‐Galeon.log -‐0.01276952 -‐1075.397269


S14

S14

Tsabd→abdc 035-‐TS-‐C7-‐8-‐COin-‐Ph-‐C11-‐12in-‐Galeon.log -‐0.01247478 -‐1075.444721 Tsacb→acbd 035-‐TS-‐C7-‐8-‐11-‐12in-‐COin-‐Ph-‐Galeon.log -‐0.01277017 -‐1075.397273 Tsacd→acdb 035-‐TS-‐C7-‐8-‐11-‐12out-‐Ph-‐COin-‐Galeon.log -‐0.01142502 -‐1075.459002 Tsadb→adbc 035-‐TS2-‐C7-‐8-‐Ph-‐COin-‐C11-‐12out-‐Galeon.log -‐0.01247457 -‐1075.444721 Tsadc→adcb 035-‐TS-‐C7-‐8-‐Ph-‐C11-‐12in-‐COout-‐Galeon.log -‐0.01261334 -‐1075.455937 Tsbac→bacd 035-‐TS-‐COin-‐C7-‐8out-‐11-‐12out-‐Ph-‐Galeon.log -‐0.01276981 -‐1075.397277 Tsbad→badc 035-‐TS-‐COin-‐C7-‐8out-‐Ph-‐C11-‐12out-‐Galeon.log -‐0.01236761 -‐1075.4421 Tsbca→bcad 035-‐TS-‐COout-‐C11-‐12out-‐7-‐8-‐Ph-‐Galeon.log -‐0.01277005 -‐1075.397273 Tsbcd→bcda 035-‐TS-‐COout-‐C11-‐12out-‐Ph-‐C7-‐8-‐Galeon.log -‐0.0106583 -‐1075.457986 Tsbda→bdac 035-‐TS-‐COin-‐Ph-‐C7-‐8-‐11-‐12out-‐Galeon.log -‐0.01236779 -‐1075.442101 Tsbdc→bdca 035-‐TS-‐COout-‐Ph-‐C11-‐12in-‐7-‐8-‐Galeon.log -‐0.01065832 -‐1075.457988 Tscab→cabd 035-‐TS-‐C11-‐12in-‐7-‐8-‐COin-‐Ph-‐Galeon.log -‐0.01276998 -‐1075.397275 Tscad→cadb 035-‐TS-‐C11-‐12in-‐7-‐8-‐Ph-‐COout-‐Galeon.log -‐0.01261302 -‐1075.455936 Tscba→cbad 035-‐TS-‐C11-‐12in-‐Coin-‐C7-‐8-‐Ph-‐Galeon.log -‐0.01277013 -‐1075.397273 Tscbd→cbda 035-‐TS-‐C11-‐12in-‐Coin-‐Ph-‐C7-‐8-‐Galeon.log -‐0.01065816 -‐1075.457986 Tscda→cdab 035-‐TS1-‐C11-‐12out-‐Ph-‐C7-‐8-‐COin-‐Galeon.log -‐0.0113678 -‐1075.458065 Tscdb→cdba 035-‐TS-‐C11-‐12out-‐Ph-‐COin-‐C7-‐8-‐Galeon.log -‐0.01065846 -‐1075.457987 Tsdab→dabc 035-‐TS-‐Ph-‐C7-‐8in-‐COin-‐C11-‐12in-‐Galeon.log -‐0.01247492 -‐1075.444721 Tsdac→dacb 035-‐TS-‐Ph-‐C7-‐8in-‐11-‐12in-‐COin-‐Galeon.log -‐0.01261339 -‐1075.455937 Tsdba→dbac 035-‐TS-‐Ph-‐COin-‐C7-‐8-‐11-‐12out-‐Galeon.log -‐0.01247421 -‐1075.444721 Tsdbc→dbca 035-‐TS-‐Ph-‐COout-‐C11-‐12out-‐C7-‐8-‐Galeon.log -‐0.01065705 -‐1075.457989 Tsdca→dcab 035-‐TS1-‐Ph-‐C11-‐12in-‐7-‐8out-‐COin-‐Galeon.log -‐0.01136771 -‐1075.458065 Tsdcb→dcba 035-‐TS2-‐Ph-‐C11-‐12-‐COin-‐C7-‐8-‐Galeon.log -‐0.01065841 -‐1075.457986 ent-‐Galeon 040-‐GS2-‐C7-‐8-‐Ph-‐COin-‐C11-‐12out-‐Galeon.log -‐0.01053577 -‐1075.469531

4.3 Tautomers of 9’-Desmethylgarugamblin I

Description File ∆Gsol MP2Limit Keto tautomer diCO-‐9-‐Desmethylgarugamblin-‐1-‐1-‐1.log -‐0.01354833 -1074.245878 C9-‐E tautomer E1-‐9-‐desmethylgarugamblin-‐1-‐10-‐1.log -‐0.01403307 -1074.238021 C11-‐E tautomer E2-‐9-‐Desmethylgarugamblin-‐1-‐1-‐1.log -‐0.01464942 -1074.233616 C9-‐Z tautomer Z1-‐9-‐desmethylgarugamblin-‐1-‐1-‐1.log -‐0.01109275 -1074.254518 C11-‐Z tautomer Z2-‐9-‐Desmethylgarugamblin-‐1-‐4-‐1.log -‐0.01095145 -1074.25362


S15

S15

4.4 Model Systems for Classical and Non-classical Hydrogen Bonding

File ∆Gsol MP2Limit Dimethoxy-‐enol-‐0002.log -‐0.009778562 -‐653.9581896 Dimethoxy-‐ketoneCoor-‐retry2.log -‐0.010754335 -‐693.2657485 Dimethoxybenzene.log -‐0.006705453 -‐500.2375408 E-‐vinyligous-‐ester.log -‐0.009326858 -‐345.5505011 E-‐vinyligous-‐ester-‐rotation-‐TS-‐04.log -‐0.010818982 -‐345.5388434 E-‐vinyligous-‐ester-‐2.log -‐0.012945402 -‐345.5442663 Monomethoxy-‐enol-‐0004.log -‐0.007282978 -‐539.5063702 Monomethoxy-‐ketoneCoor-‐retry3.log -‐0.008614415 -‐578.8139709 Monomethoxybenzene.log -‐0.003995437 -‐385.7869887 Z-‐vinyligous-‐ester-‐retry.log -‐0.005831009 -‐345.5675104 Z-‐vinyligous-‐ester-‐2.log -‐0.012089769 -‐345.5492674 Z-‐vinyligous-‐ester-‐rotation-‐TS.log -‐0.008259834 -‐345.5415757 enol.log -‐0.004748697 -‐153.7157386 ketone.log -‐0.006298885 -‐193.0234847

Figure 5 H(MP2+Gcor+Gsol) ∆H (kcal/mol) E-‐vinyligous-‐ester.log -‐345.427518 8.4 E-‐vinyligous-‐ester-‐rotation-‐TS -‐345.4191924 13.7 E-‐vinyligous-‐ester-‐2.log -‐345.4248017 10.1 Z-‐vinyligous-‐ester-‐retry.log -‐345.4409714 0.0 Z-‐vinyligous-‐ester-‐rotation-‐TS.log -‐345.4290271 7.5 Z-‐vinyligous-‐ester-‐2.log -‐345.4190955 13.7

Figure 6

Models for C9-‐(E/Z)-‐9-‐desmethylgarugamblin I H(MP2+Gcor+Gsol) ∆H (kcal/mol) Dimethoxybenzene+ketone -‐692.9773598 0.0 Dimethoxy-‐ketoneCoor-‐retry2.log -‐692.9777228 -‐0.2 Monomethoxybenzene+enol -‐539.2793715 0.0 Monomethoxy-‐enol-‐0003.log -‐539.2794531 -‐0.1 Models for C11-‐(E/Z)-‐9-‐desmethylgarugamblin I H(MP2+Gcor+Gsol) ∆H (kcal/mol) Dimethoxybenzene+enol -‐653.6972136 0.0 Dimethoxy-‐enol-‐0001.log -‐653.6983682 -‐0.7 Monomethoxybenzene+ketone -‐578.5595177 0.0 Monomethoxy-‐ketoneCoor-‐retry3.log -‐578.5591653 0.2


S16

S16

4.5 C9-Z-9’-Desmethylgarugamblin I

Description File ∆Gsol MP2Limit C9-‐Z-‐9-‐desmethyl garugamblin I

Z-‐9-‐desmethylgarugamblin-‐a-‐mAnsa-‐a-‐GS.log -‐0.01109271 -‐1074.254518

TSa Z-‐9-‐desmethylgarugamblin-‐a-‐mAnsa-‐b-‐TS.log -‐0.01216141 -‐1074.241212

Inta Z-‐9-‐desmethylgarugamblin-‐a-‐mAnsa-‐c-‐GS.log -‐0.01164259 -‐1074.251468

TSa→ab Z-‐9-‐desmethylgarugamblin-‐a-‐mAnsa-‐CO-‐d-‐TS.log -‐0.01149859 -‐1074.240536

Intab Z-‐9-‐desmethylgarugamblin-‐a-‐mAnsa-‐CO-‐e-‐GS.log -‐0.01156685 -‐1074.246532

TSab→abc Z-‐9-‐desmethylgarugamblin-‐a-‐mAnsa-‐CO-‐f-‐TS.log -‐0.01138742 -‐1074.245214

ent-‐C9-‐Z-‐9-‐desmethyl garugamblin I

Z-‐9-‐desmethylgarugamblin-‐a-‐mAnsa-‐CO-‐g-‐GS.log -‐0.0110926 -‐1074.254516

TSa→ac Z-‐9-‐desmethylgarugamblin-‐a-‐mAnsa-‐pAnsa-‐d-‐TS.log -‐0.01149838 -‐1074.240535

Intac Z-‐9-‐desmethylgarugamblin-‐a-‐mAnsa-‐pAnsa-‐e-‐GS.log -‐0.01156677 -‐1074.246528

TSac→acb Z-‐9-‐desmethylgarugamblin-‐a-‐mAnsa-‐pAnsa-‐f-‐TS.log -‐0.01138747 -‐1074.245213

TSbc Z-‐9-‐desmethylgarugamblin-‐b-‐CO-‐b-‐TS.log -‐0.01179447 -‐1074.233469 Intbc Z-‐9-‐desmethylgarugamblin-‐b-‐CO-‐c-‐GS.log -‐0.01164289 -‐1074.25147

TSbc→bca Z-‐9-‐desmethylgarugamblin-‐b-‐CO-‐mAnsa-‐d-‐TS.log -‐0.01216135 -‐1074.241213

TSc Z-‐9-‐desmethylgarugamblin-‐c-‐pAnsa-‐b-‐TS.log -‐0.01138737 -‐1074.245213

Intc Z-‐9-‐desmethylgarugamblin-‐c-‐pAnsa-‐c-‐GS.log -‐0.01156672 -‐1074.246528

TSc→cb Z-‐9-‐desmethylgarugamblin-‐c-‐pAnsa-‐CO-‐d-‐TS.log -‐0.0114983 -‐1074.240536

Intcb Z-‐9-‐desmethylgarugamblin-‐c-‐pAnsa-‐CO-‐e-‐GS.log -‐0.01164193 -‐1074.251473

TScb→cba Z-‐9-‐desmethylgarugamblin-‐c-‐pAnsa-‐CO-‐mAnsa-‐f-‐TS.log -‐0.01216148 -‐1074.241213

TSca→cab Z-‐9-‐desmethylgarugamblin-‐c-‐pAnsa-‐mAnsa-‐Co-‐h-‐TS.log -‐0.01149849 -‐1074.240536

TSc→ca Z-‐9-‐desmethylgarugamblin-‐c-‐pAnsa-‐mAnsa-‐d-‐TS.log -‐0.01216151 -‐1074.241211

Intca Z-‐9-‐desmethylgarugamblin-‐c-‐pAnsa-‐mAnsa-‐g-‐GS.log -‐0.01164341 -‐1074.251475


S17

S17

4.6 C9-E-9’-Desmethylgarugamblin I

Description File ∆Gsol MP2Limit C9-‐E-‐9-‐desmethyl garugamblin I

E-‐9-‐desmethylgarugamblin-‐a-‐mAnsa-‐a-‐GS.log -‐0.01403315 -‐1074.23802

TSa E-‐9-‐desmethylgarugamblin-‐a-‐mAnsa-‐b-‐TS.log -‐0.01401533 -‐1074.2211

Inta E-‐9-‐desmethylgarugamblin-‐a-‐mAnsa-‐c-‐GS.log -‐0.01458522 -‐1074.23592

Intab E-‐9-‐desmethylgarugamblin-‐a-‐mAnsa-‐CO-‐c-‐scanIn-‐switchAtoms-‐GS.log -‐0.0159219 -‐1074.224748

TSa→ab E-‐9-‐desmethylgarugamblin-‐a-‐mAnsa-‐CO-‐c-‐scanIn-‐switchAtoms-‐TS1.log -‐0.01397639 -‐1074.176636

ent-‐C9-‐E-‐9-‐desmethyl garugamblin I

E-‐9-‐desmethylgarugamblin-‐a-‐mAnsa-‐pAnsa-‐c-‐scanIn-‐switchAtoms-‐GS.log -‐0.01403342 -‐1074.23802

TSa→acb E-‐9-‐desmethylgarugamblin-‐a-‐mAnsa-‐pAnsa-‐c-‐scanIn-‐switchAtoms-‐TS.log -‐0.01505578 -‐1074.165988

TSb E-‐9-‐desmethylgarugamblin-‐b-‐CO-‐b-‐TS.log -‐0.01522593 -‐1074.216439

Intb E-‐9-‐desmethylgarugamblin-‐b-‐CO-‐c-‐GS.log -‐0.01592283 -‐1074.224748

TSb→ba E-‐9-‐desmethylgarugamblin-‐b-‐CO-‐mAnsa-‐c-‐scanIn-‐TS1.log -‐0.01585286 -‐1074.215914

Intbc ≋ Intc E-‐9-‐desmethylgarugamblin-‐b-‐CO-‐pAnsa-‐c-‐scanIn-‐GS.log -‐0.01592325 -‐1074.22475

TSb→bc E-‐9-‐desmethylgarugamblin-‐b-‐CO-‐pAnsa-‐c-‐scanIn-‐TS.log -‐0.01605209 -‐1074.194647

TSc→cb E-‐9-‐desmethylgarugamblin-‐c-‐pAnsa-‐CO-‐c-‐scanIn-‐afterbackSM-‐TS.log -‐0.01522573 -‐1074.21644

Intcb ≋ Intb E-‐9-‐desmethylgarugamblin-‐c-‐pAnsa-‐CO-‐c-‐scanIn-‐GS.log -‐0.01592246 -‐1074.224748

TSc E-‐9-‐desmethylgarugamblin-‐c-‐pAnsa-‐CO-‐mAnsa-‐b2-‐TS.log -‐0.01403413

-1074.198154

Intc E-‐9-‐desmethylgarugamblin-‐c-‐pAnsa-‐CO-‐mAnsa-‐e-‐GS.log -‐0.01384273 -1074.21064

TSc→ca E-‐9-‐desmethylgarugamblin-‐c-‐pAnsa-‐CO-‐mAnsa-‐f-‐QST2TS.log -‐0.01361523

-1074.210319

Intca E-‐9-‐desmethylgarugamblin-‐c-‐pAnsa-‐CO-‐mAnsa-‐g-‐GS.log -‐0.0145854

-1074.235918

TSca→cab E-‐9-‐desmethylgarugamblin-‐c-‐pAnsa-‐CO-‐mAnsa-‐h-‐TS.log -‐0.01537086 -1074.2214


S18

S18

4.7 C9-E-Garugamblin I

Description File ∆Gsol MP2Limit C9-‐E-‐

Garugamblin I E-‐Garugamblin-‐a-‐mAnsa-‐CO-‐pAnsa-‐a-‐GS.log -‐0.01263009 -‐1113.50449 TSa E-‐Garugamblin-‐a-‐mAnsa-‐CO-‐pAnsa-‐b-‐TS.log -‐0.01252996 -‐1113.488133 Inta E-‐Garugamblin-‐a-‐mAnsa-‐CO-‐pAnsa-‐c-‐GS.log -‐0.01308181 -‐1113.502623

TSa→ab E-‐Garugamblin-‐a-‐mAnsa-‐CO-‐pAnsa-‐d-‐TS.log -‐0.01350451 -‐1113.487183 Intab E-‐Garugamblin-‐a-‐mAnsa-‐CO-‐pAnsa-‐e-‐GS.log -‐0.01451815 -‐1113.490203

TSab→abc E-‐Garugamblin-‐a-‐mAnsa-‐CO-‐pAnsa-‐f2-‐TS.log -‐0.01396587 -‐1113.466584 ent-‐C9-‐E-‐

Garugamblin I E-‐Garugamblin-‐a-‐mAnsa-‐CO-‐pAnsa-‐i-‐GS.log -‐0.01262968 -‐1113.504493 TSa→acb E-‐Garugamblin-‐a-‐mAnsa-‐pAnsa-‐CO-‐d-‐TS.log -‐0.01236702 -‐1113.476087 TSb E-‐Garugamblin-‐b-‐CO-‐mAnsa-‐pAnsa-‐b3-‐TS.log -‐0.01416675 -‐1113.482034 Intb E-‐Garugamblin-‐b-‐CO-‐mAnsa-‐pAnsa-‐c-‐GS.log -‐0.0145153 -‐1113.490205

TSb→ba E-‐Garugamblin-‐b-‐CO-‐mAnsa-‐pAnsa-‐d-‐TS.log -‐0.0141702 -‐1113.482417 Intba E-‐Garugamblin-‐b-‐CO-‐mAnsa-‐pAnsa-‐e-‐GS.log -‐0.01459475 -‐1113.490361

TSba→bac E-‐Garugamblin-‐b-‐CO-‐mAnsa-‐pAnsa-‐f2-‐TS.log -‐0.01257339 -‐1113.465899

TSb→bac E-‐Garugamblin-‐b-‐CO-‐pAnsa-‐mAnsa-‐idenCO-‐mAnsa-‐pAnsa-‐d3-‐TS-‐.log -‐0.01257223 -‐1113.465896

TSc E-‐Garugamblin-‐c-‐pAnsa-‐CO-‐mAnsa-‐b2-‐TS.log -‐0.0125724 -‐1113.465897 Intc E-‐Garugamblin-‐c-‐pAnsa-‐CO-‐mAnsa-‐e-‐GS.log -‐0.01227203 -‐1113.477975

Tsc→cb E-‐Garugamblin-‐c-‐pAnsa-‐CO-‐mAnsa-‐f-‐QST2TS.log -‐0.01204194 -‐1113.477332 Intcb E-‐Garugamblin-‐c-‐pAnsa-‐CO-‐mAnsa-‐g-‐GS.log -‐0.01308249 -‐1113.502621

TScb→cba E-‐Garugamblin-‐c-‐pAnsa-‐CO-‐mAnsa-‐h-‐TS.log -‐0.01391166 -‐1113.487923

Tsc→ca E-‐Garugamblin-‐c-‐pAnsa-‐mAnsa-‐CO-‐idenpAnsa-‐CO-‐mAnsa-‐f2-‐TS.log -‐0.01372498 -‐1113.483184

Intca E-‐Garugamblin-‐c-‐pAnsa-‐mAnsa-‐CO-‐idenpAnsa-‐CO-‐mAnsa-‐g-‐GS.log -‐0.01308181 -‐1113.502622

TSca→cab E-‐Garugamblin-‐c-‐pAnsa-‐mAnsa-‐CO-‐idenpAnsa-‐CO-‐mAnsa-‐h-‐TS.log -‐0.01391161 -‐1113.487923


S19

S19


Description File ∆Gsol MP2Limit C11-‐E-‐

Garugamblin I a-‐000-‐E-‐Garugamblin-‐1.log -‐0.01307118 -‐1113.500527 TSa a-‐005-‐mAnsa-‐pCO-‐E-‐Garugamblin-‐1.log -‐0.01280387 -‐1113.493923 Inta a-‐010-‐mAnsa-‐pCO-‐E-‐Garugamblin-‐1.log -‐0.0129152 -‐1113.495688

TSa→abc a-‐015-‐mAnsa-‐CO2-‐pCO-‐E-‐Garugamblin-‐1.log -‐0.01162625 -‐1113.480986 TSa→ac a-‐015-‐mAnsa-‐pAnsa-‐pCO-‐E-‐Garugamblin-‐1.log -‐0.01305636 -‐1113.491631

ent-‐C11-‐E-‐Garugamblin I a-‐020-‐mAnsa-‐CO2-‐pCO-‐E-‐Garugamblin-‐1.log -‐0.0130747 -‐1113.500524

TSac→acb a-‐020-‐mAnsa-‐pAnsa-‐CO-‐pCO-‐E-‐Garugamblin-‐1-‐TS2.log -‐0.01162635 -‐1113.480987

Intac a-‐020-‐mAnsa-‐pAnsa-‐pCO-‐E-‐Garugamblin-‐1.log -‐0.01332822 -‐1113.494011 TSb b-‐005-‐CO-‐pCO-‐E-‐Garugamblin-‐1-‐plus1.log -‐0.01162635 -‐1113.480992 Intb b-‐010-‐CO-‐pCO-‐E-‐Garugamblin-‐1-‐plus1.log -‐0.01232659 -‐1113.488903

TSb→ba b-‐015-‐CO-‐mAnsa1-‐pCO-‐E-‐Garugamblin-‐1.log -‐0.01330669 -‐1113.478825

TSba→bac b-‐020-‐CO-‐mAnsa2-‐pAnsa-‐pCO-‐E-‐Garugamblin-‐1-‐TS.log -‐0.01336018 -‐1113.495706

Intba b-‐020-‐CO-‐mAnsa2-‐pCO-‐E-‐Garugamblin-‐1.log -‐0.01372942 -‐1113.497943 TSb→bc b-‐015-‐CO-‐pAnsa-‐pCO-‐E-‐Garugamblin-‐1.log -‐0.01230006 -‐1113.484689

TSbc→bca b-‐020-‐CO-‐pAnsa-‐mAnsa-‐pCO-‐E-‐Garugamblin-‐1-‐TS.log -‐0.01267008 -‐1113.477379

Intbc b-‐020-‐CO-‐pAnsa-‐pCO-‐E-‐Garugamblin-‐1.log -‐0.01244535 -‐1113.490339 TSc c-‐005-‐pAnsa-‐pCO-‐E-‐Garugamblin-‐1.log -‐0.01336047 -‐1113.495706 Intc c-‐010-‐pAnsa-‐pCO-‐E-‐Garugamblin-‐1.log -‐0.01372929 -‐1113.497939

TSc→cb c-‐015-‐pAnsa-‐CO-‐pCO-‐E-‐Garugamblin-‐1.log -‐0.01185923 -‐1113.47976 TSc→ca c-‐015-‐pAnsa-‐mAnsa2-‐pCO-‐E-‐Garugamblin-‐1.log -‐0.01330686 -‐1113.478826

TScb→cba c-‐020-‐pAnsa-‐CO-‐mAnsa-‐pCO-‐E-‐Garugamblin-‐1-‐TS.log -‐0.01267013 -‐1113.477378

Intcb c-‐020-‐pAnsa-‐CO-‐pCO-‐E-‐Garugamblin-‐1.log -‐0.01244547 -‐1113.490345

TSca→cab c-‐020-‐pAnsa-‐mAnsa2-‐CO-‐pCO-‐E-‐Garugamblin-‐1-‐TS.log -‐0.01162632 -‐1113.480987

Intca c-‐020-‐pAnsa-‐mAnsa2-‐pCO-‐E-‐Garugamblin-‐1.log -‐0.01232593 -‐1113.488906


S20

S20

5 Coordinates, Energies, and Thermal Corrections of All Structures Reported in the Manuscript and listed by the Reactions

5.1 Acerogenin L

5.1.1 Acerogenin L Supporting Information: CO-mAnsa-pAnsa-000-acerogenin-L.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -961.730175442 Predicted Change= -3.384862D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00057 || 0.00180 [ YES ] 0.00057 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.747678 -1.944744 -1.110611 H 2.162395 -1.959272 -2.116326 C 0.377794 -2.127990 -0.936832 H -0.282473 -2.272330 -1.786848 C -0.161998 -2.065401 0.348984 O -1.546422 -2.075804 0.518331 C -2.163796 -0.847398 0.262200 C 0.662816 -1.922111 1.459307 H 0.224606 -1.900379 2.452177 C 2.032096 -1.725159 1.266429 H 2.669269 -1.556548 2.130935 C 2.588691 -1.679732 -0.017576 C -1.546786 0.380997 0.461585 H -0.543291 0.407366 0.868749 C -2.206628 1.576154 0.140401 C -1.496598 2.908812 0.296555 H -2.175120 3.709548 -0.017372 C -0.184289 3.019677 -0.514758 H 0.069379 4.082951 -0.645276 H -0.310461 2.605261 -1.521599 C 1.036360 2.396670 0.173598 C 2.033865 1.672767 -0.721035 H 2.204897 2.274868 -1.625621 H 1.505338 0.775633 -1.076636 C 3.361357 1.289581 -0.049565 H 3.152658 0.969374 0.976691 H 3.977135 2.192223 0.042710 C 4.150198 0.193801 -0.810648 H 3.838798 0.178904 -1.864042 H 5.218144 0.444766 -0.820552 C 4.021586 -1.238818 -0.224969 H 4.545820 -1.934470 -0.893944 H 4.548554 -1.273641 0.736492 O 1.182259 2.473444 1.381001 H -1.249119 3.095793 1.348906 C -3.515055 1.491255 -0.348351 H -4.051774 2.400995 -0.606506 C -4.151876 0.258126 -0.517128 H -5.166340 0.196755 -0.898943 C -3.478029 -0.925426 -0.222525 O -4.080239 -2.133839 -0.414401 H -3.427513 -2.814558 -0.172812 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -961.730175442 Predicted Change= -3.384862D-09 Zero-point correction (ZPE)= -961.3790 0.35108 Internal Energy (U)= -961.3603 0.36984 Enthalpy (H)= -961.3593 0.37078 Gibbs Free Energy (G)= -961.4260 0.30416 ------------------------------------------------------------------------------

Frequencies -- 22.4168 54.7287 60.4629

5.1.2 TSa Supporting Information: mAnsa-CO-pAnsa-005-Acerogenin-L-TSmAnsa.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -961.711163723 Predicted Change= -8.638282D-11 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00015 || 0.00180 [ YES ] 0.00015 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.452361 -2.196315 -0.961483 H 1.689220 -2.418612 -1.999828 C 0.139579 -2.327642 -0.519445 H -0.652195 -2.636066 -1.196036 C -0.176488 -1.964174 0.791489 O -1.522104 -1.835796 1.167633 C -2.097478 -0.728050 0.523988 C 0.820868 -1.615091 1.693802 H 0.557313 -1.365851 2.716710 C 2.133357 -1.485383 1.233008 H 2.900133 -1.135238 1.918807 C 2.454407 -1.699734 -0.112570 C -1.579627 0.556769 0.667781 H -0.766634 0.708967 1.367894 C -2.066251 1.608359 -0.115618 C -1.555543 3.039512 -0.026038 H -1.801769 3.525225 -0.976221 C -0.056228 3.375982 0.315479 H -0.032203 3.944681 1.248537 H 0.321480 4.038494 -0.474652 C 1.002427 2.284807 0.511921 C 1.570886 1.529359 -0.690967 H 1.325488 2.047771 -1.625903 H 1.035725 0.571819 -0.723380 C 3.093187 1.286037 -0.568218 H 3.320552 1.113922 0.488824 H 3.609587 2.214693 -0.842819 C 3.655802 0.123664 -1.421949 H 3.043338 -0.010662 -2.323829 H 4.659580 0.390827 -1.776530 C 3.776000 -1.237597 -0.681894 H 4.176759 -1.979951 -1.384827 H 4.512103 -1.135813 0.125277 O 1.424811 2.058383 1.634346 H -2.160888 3.564934 0.724519 C -3.131692 1.330028 -0.989089 H -3.533183 2.128463 -1.609012 C -3.695733 0.059540 -1.085978 H -4.515680 -0.142294 -1.768259 C -3.166464 -0.993096 -0.336640 O -3.651086 -2.259019 -0.476438 H -3.141920 -2.815704 0.140932 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -961.711163723 Predicted Change= -8.638282D-11 Zero-point correction (ZPE)= -961.3600 0.35113 Internal Energy (U)= -961.3419 0.36917 Enthalpy (H)= -961.3410 0.37011 Gibbs Free Energy (G)= -961.4058 0.30533 ------------------------------------------------------------------------------ Frequencies -- -168.0887 28.3346 53.4296

5.1.3 TSb Supporting Information: CO-mAnsa-pAnsa-005-acerogenin-L-TSco.log ------------------------------------------------------------------------------


S21

S21

Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -961.718762765 Predicted Change= 3.313094D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00097 || 0.00180 [ YES ] 0.00097 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.329431 -2.078309 -1.252252 H 1.756574 -1.961545 -2.245836 C -0.054514 -2.117305 -1.107855 H -0.711689 -2.016190 -1.966405 C -0.604866 -2.202975 0.172101 O -1.975032 -1.990416 0.346640 C -2.332019 -0.641280 0.250424 C 0.211339 -2.377581 1.284706 H -0.238409 -2.472320 2.268407 C 1.599409 -2.325888 1.123243 H 2.237870 -2.395784 2.000651 C 2.177426 -2.104991 -0.132720 C -1.465095 0.396993 0.563659 H -0.478071 0.156555 0.932729 C -1.834386 1.734421 0.380052 C -0.818463 2.836109 0.624836 H -1.345231 3.793145 0.698117 C 0.278430 2.977809 -0.488247 H 0.336098 4.015844 -0.827088 H -0.017270 2.371039 -1.354874 C 1.718221 2.587398 -0.126471 C 1.978574 1.165507 0.381671 H 1.394560 0.478864 -0.238713 H 1.520787 1.103040 1.379003 C 3.467496 0.756194 0.442446 H 3.707098 0.375100 1.443412 H 4.058856 1.668823 0.312451 C 3.923218 -0.279814 -0.608742 H 3.474603 -0.035171 -1.581618 H 5.007934 -0.180132 -0.745126 C 3.646700 -1.772064 -0.277874 H 4.094387 -2.382712 -1.073668 H 4.174834 -2.031739 0.648562 O 2.620289 3.391823 -0.274010 H -0.337975 2.687987 1.600690 C -3.131548 1.995163 -0.077045 H -3.455226 3.022368 -0.226365 C -4.024815 0.955068 -0.353795 H -5.029765 1.159512 -0.710127 C -3.630990 -0.375111 -0.205437 O -4.488619 -1.390139 -0.510099 H -4.004364 -2.222906 -0.370656 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -961.718762765 Predicted Change= 3.313094D-10 Zero-point correction (ZPE)= -961.3676 0.35113 Internal Energy (U)= -961.3496 0.36908 Enthalpy (H)= -961.3487 0.37003 Gibbs Free Energy (G)= -961.4132 0.30548 ------------------------------------------------------------------------------ Frequencies -- -27.5273 27.5577 46.1535

5.1.4 TSc Supporting Information: pAnsa-CO-mAnsa-Acerogenin-L-d-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1

------------------------------------------------------------------------------ SCF Energy= -961.717342236 Predicted Change= -9.739254D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00059 || 0.00180 [ YES ] 0.00059 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.386110 -1.909349 -1.348208 H 1.714498 -1.849599 -2.383756 C 0.031097 -2.078798 -1.073970 H -0.700850 -2.130207 -1.874361 C -0.397670 -2.081274 0.252240 O -1.760756 -1.986490 0.535654 C -2.275328 -0.705539 0.303521 C 0.523149 -2.046361 1.295140 H 0.168622 -2.069430 2.320913 C 1.877467 -1.873824 1.002875 H 2.580624 -1.780514 1.825712 C 2.323316 -1.733273 -0.318592 C -1.506287 0.448705 0.381967 H -0.470499 0.370866 0.685112 C -2.048483 1.700001 0.064673 C -1.167186 2.937038 0.080049 H -1.727344 3.773133 -0.352909 C 0.165522 2.778993 -0.686768 H 0.528394 3.771670 -0.997323 H 0.026143 2.210078 -1.614170 C 1.315716 2.176350 0.126902 C 2.456480 1.536639 -0.672290 H 2.668763 2.182901 -1.535063 H 2.026585 0.626288 -1.106445 C 3.729900 1.253804 0.157727 H 3.507109 1.566206 1.182099 H 4.514332 1.930923 -0.197225 C 4.338075 -0.189363 0.218250 H 5.400695 -0.120957 -0.044621 H 4.327888 -0.522519 1.262652 C 3.750685 -1.328988 -0.645497 H 3.805568 -1.060827 -1.708472 H 4.417627 -2.195344 -0.524583 O 1.320307 2.221157 1.343630 H -0.922131 3.219860 1.111656 C -3.402812 1.755648 -0.284757 H -3.854354 2.711639 -0.538935 C -4.191886 0.601844 -0.322991 H -5.240586 0.647834 -0.600351 C -3.632691 -0.644143 -0.041352 O -4.387783 -1.777837 -0.119408 H -3.796263 -2.525297 0.077543 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -961.717342236 Predicted Change= -9.739254D-10 Zero-point correction (ZPE)= -961.3662 0.35105 Internal Energy (U)= -961.3482 0.36911 Enthalpy (H)= -961.3472 0.37005 Gibbs Free Energy (G)= -961.4124 0.30487 ------------------------------------------------------------------------------ Frequencies -- -138.3910 22.7982 38.0708

5.1.5 Inta Supporting Information: mAnsa-CO-pAnsa-010-Acerogenin-L.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -961.724542499 Predicted Change= -3.329477D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00438 || 0.00180 [ NO ] 0.00438 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms)


S22

S22

Type X Y Z ------------------------------------------------------------------------------ C 2.038221 -2.166732 -1.060355 H 2.690552 -2.308213 -1.919427 C 0.675930 -2.450335 -1.186553 H 0.255402 -2.795891 -2.126087 C -0.168809 -2.199334 -0.108188 O -1.555391 -2.236849 -0.295327 C -2.117914 -0.956090 -0.304831 C 0.346811 -1.791705 1.120813 H -0.325544 -1.620025 1.955653 C 1.707392 -1.517347 1.231264 H 2.097421 -1.149359 2.176411 C 2.563360 -1.634377 0.126177 C -1.458873 0.145782 -0.835639 H -0.497472 -0.001155 -1.312529 C -1.995974 1.431450 -0.733353 C -1.172262 2.615155 -1.200714 H -0.545542 2.313987 -2.049657 C -0.279357 3.246998 -0.098190 H -0.902747 3.604004 0.727254 H 0.227120 4.121787 -0.534988 C 0.808271 2.370626 0.530685 C 1.849195 1.707793 -0.377650 H 1.995220 2.308416 -1.285658 H 1.405818 0.762172 -0.714136 C 3.191007 1.425644 0.324473 H 2.978503 1.121336 1.354300 H 3.742955 2.370734 0.402186 C 4.082091 0.370586 -0.376016 H 3.870348 0.357762 -1.454168 H 5.134283 0.667357 -0.280665 C 3.968029 -1.076062 0.180125 H 4.654157 -1.717337 -0.388254 H 4.322921 -1.077907 1.218492 O 0.853943 2.228654 1.739438 H -1.832682 3.407402 -1.573882 C -3.258391 1.568029 -0.140689 H -3.709902 2.553238 -0.050819 C -3.950629 0.457489 0.347689 H -4.927492 0.563690 0.809299 C -3.379594 -0.816116 0.286288 O -4.033815 -1.893197 0.805077 H -3.442237 -2.659580 0.701148 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -961.724542499 Predicted Change= -3.329477D-08 Zero-point correction (ZPE)= -961.3732 0.35132 Internal Energy (U)= -961.3545 0.37001 Enthalpy (H)= -961.3535 0.37096 Gibbs Free Energy (G)= -961.4200 0.30449 ------------------------------------------------------------------------------ Frequencies -- 28.1404 39.5263 57.4162

5.1.6 Intb Supporting Information: CO-mAnsa-pAnsa-010-acerogenin-L.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -961.722066411 Predicted Change= -3.748755D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00087 || 0.00180 [ YES ] 0.00087 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.517546 -1.663086 1.186013 H -1.925457 -1.361617 2.146547 C -0.148728 -1.874280 1.071630 H 0.511474 -1.722704 1.920029 C 0.394132 -2.175153 -0.177736 O 1.780919 -2.098230 -0.355540 C 2.235590 -0.776683 -0.294685

C -0.429323 -2.399215 -1.275660 H 0.011901 -2.655436 -2.234123 C -1.805556 -2.182110 -1.143610 H -2.445022 -2.292392 -2.016596 C -2.359255 -1.740855 0.064731 C 1.473261 0.298818 -0.731888 H 0.510807 0.104772 -1.187303 C 1.908563 1.615543 -0.562392 C 0.984190 2.754410 -0.946702 H 1.574114 3.661685 -1.123404 C -0.086701 3.107306 0.122328 H -0.605026 4.019392 -0.214347 H 0.398380 3.339050 1.075363 C -1.188152 2.084731 0.432453 C -2.029666 1.539408 -0.722703 H -1.566721 0.599357 -1.046085 H -1.945360 2.221902 -1.578873 C -3.529837 1.308268 -0.421004 H -4.022983 1.102180 -1.381812 H -3.950285 2.259609 -0.068528 C -3.946720 0.218997 0.591485 H -3.417538 0.388002 1.532926 H -5.013353 0.377571 0.801540 C -3.793426 -1.261576 0.158110 H -4.339124 -1.874502 0.889467 H -4.296815 -1.416771 -0.805599 O -1.410259 1.766564 1.588183 H 0.487779 2.524487 -1.898485 C 3.172643 1.818239 0.005462 H 3.546170 2.829656 0.146957 C 3.967306 0.739144 0.402747 H 4.946115 0.896562 0.845260 C 3.500565 -0.570385 0.271206 O 4.255465 -1.621398 0.699462 H 3.723892 -2.425418 0.561519 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -961.722066411 Predicted Change= -3.748755D-09 Zero-point correction (ZPE)= -961.3707 0.35131 Internal Energy (U)= -961.3521 0.36992 Enthalpy (H)= -961.3512 0.37086 Gibbs Free Energy (G)= -961.4171 0.30495 ------------------------------------------------------------------------------ Frequencies -- 27.7589 54.6550 59.3662

5.1.7 Intc Supporting Information: pAnsa-CO-mAnsa-Acerogenin-L-e-GS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -961.727642473 Predicted Change= -5.065334D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00074 || 0.00180 [ YES ] 0.00074 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.535924 -1.915576 -1.226530 H 1.994780 -1.818661 -2.208203 C 0.151890 -2.067664 -1.131421 H -0.476001 -2.065692 -2.017327 C -0.438048 -2.133465 0.128491 O -1.823889 -2.025568 0.246687 C -2.282502 -0.706386 0.179829 C 0.343896 -2.178043 1.280201 H -0.137670 -2.257613 2.249888 C 1.723184 -2.013338 1.167727 H 2.327657 -1.979713 2.070951 C 2.332586 -1.807499 -0.078982 C -1.480791 0.403128 0.417024 H -0.448709 0.261306 0.710170 C -1.989044 1.701765 0.279414


S23

S23

C -1.067038 2.892424 0.470338 H -1.635614 3.812800 0.297937 C 0.163861 2.882805 -0.464253 H 0.528319 3.913715 -0.600573 H -0.106178 2.527033 -1.465788 C 1.383323 2.108415 0.054095 C 2.322808 1.560541 -1.013499 H 2.353139 2.288281 -1.837292 H 1.820424 0.678882 -1.435045 C 3.764636 1.236506 -0.578099 H 4.182113 2.138842 -0.112428 H 4.351416 1.071898 -1.493068 C 4.030165 0.061429 0.386613 H 5.091012 0.125897 0.663457 H 3.459320 0.214242 1.307572 C 3.782563 -1.376671 -0.147684 H 4.153596 -1.460074 -1.177855 H 4.391091 -2.064305 0.454612 O 1.592098 1.970594 1.247055 H -0.698786 2.934551 1.503165 C -3.336223 1.846720 -0.066964 H -3.759288 2.841654 -0.183016 C -4.155674 0.731866 -0.274129 H -5.200644 0.845627 -0.546013 C -3.635036 -0.555725 -0.162457 O -4.422687 -1.645649 -0.394449 H -3.857031 -2.431074 -0.293756 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -961.727642473 Predicted Change= -5.065334D-09 Zero-point correction (ZPE)= -961.3764 0.35122 Internal Energy (U)= -961.3577 0.36985 Enthalpy (H)= -961.3568 0.37080 Gibbs Free Energy (G)= -961.4227 0.30489 ------------------------------------------------------------------------------ Frequencies -- 30.5363 49.9727 61.5060

5.1.8 TSa→ab Supporting Information: mAnsa-CO-pAnsa-015-Acerogenin-L-TSco.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -961.720840734 Predicted Change= -1.149356D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00021 || 0.00180 [ YES ] 0.00021 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.657155 -2.471173 -1.020147 H 2.284658 -2.651011 -1.890279 C 0.271644 -2.583371 -1.145548 H -0.192090 -2.831242 -2.095494 C -0.531669 -2.272760 -0.051457 O -1.907354 -2.107953 -0.235255 C -2.278637 -0.758657 -0.250556 C 0.033292 -1.992819 1.191626 H -0.612885 -1.783711 2.038912 C 1.418750 -1.887878 1.300514 H 1.858969 -1.612109 2.255769 C 2.246206 -2.050149 0.180764 C -1.449515 0.249039 -0.732617 H -0.491226 -0.017750 -1.160035 C -1.818804 1.593957 -0.642075 C -0.851925 2.685317 -1.064856 H -0.237783 2.336311 -1.904062 C 0.056965 3.239730 0.069676 H -0.468741 3.139548 1.029768 H 0.202547 4.317187 -0.066149 C 1.479501 2.698302 0.316743 C 1.919796 1.328240 -0.194359 H 1.818949 1.322021 -1.290760 H 1.199765 0.584933 0.165591

C 3.360681 0.977443 0.215793 H 3.410509 0.889454 1.308906 H 3.988009 1.841946 -0.026777 C 3.985575 -0.274443 -0.441252 H 3.692279 -0.323628 -1.499481 H 5.075902 -0.144823 -0.438601 C 3.702160 -1.647821 0.224765 H 4.317361 -2.401337 -0.284766 H 4.047378 -1.614571 1.265994 O 2.241743 3.396016 0.962811 H -1.431141 3.531217 -1.453454 C -3.080884 1.890792 -0.108140 H -3.405026 2.926251 -0.034256 C -3.936631 0.880391 0.335855 H -4.912920 1.112857 0.749992 C -3.537655 -0.456703 0.283060 O -4.353503 -1.441345 0.754989 H -3.867615 -2.279907 0.662078 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -961.720840734 Predicted Change= -1.149356D-10 Zero-point correction (ZPE)= -961.3701 0.35072 Internal Energy (U)= -961.3521 0.36870 Enthalpy (H)= -961.3511 0.36964 Gibbs Free Energy (G)= -961.4154 0.30539 ------------------------------------------------------------------------------ Frequencies -- -43.1311 34.0471 62.6217

5.1.9 TSa→ac Supporting Information: mAnsa-pAnsa-CO-015-Acerogenin-L-TSpAnas.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -961.717342216 Predicted Change= -4.843451D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00067 || 0.00180 [ YES ] 0.00067 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.877309 -1.873832 1.002869 H -2.580458 -1.780545 1.825716 C -0.522988 -2.046374 1.295117 H -0.168451 -2.069456 2.320887 C 0.397820 -2.081264 0.252207 O 1.760911 -1.986458 0.535602 C 2.275417 -0.705471 0.303525 C -0.030963 -2.078751 -1.073997 H 0.700976 -2.130130 -1.874398 C -1.385979 -1.909314 -1.348218 H -1.714380 -1.849562 -2.383762 C -2.323178 -1.733280 -0.318590 C 1.506302 0.448719 0.382022 H 0.470524 0.370807 0.685176 C 2.048401 1.700055 0.064738 C 1.166998 2.937016 0.080131 H 0.921915 3.219787 1.111745 C -0.165687 2.778879 -0.686705 H -0.026251 2.209961 -1.614098 H -0.528612 3.771527 -0.997295 C -1.315879 2.176163 0.126913 C -2.456793 1.536810 -0.672369 H -2.027026 0.626637 -1.107023 H -2.669176 2.183471 -1.534821 C -3.730111 1.253720 0.157728 H -4.514688 1.930715 -0.197136 H -3.507280 1.566125 1.182090 C -4.338079 -0.189535 0.218279 H -4.327819 -0.522672 1.262687 H -5.400714 -0.121273 -0.044566 C -3.750576 -1.329088 -0.645478


S24

S24

H -4.417445 -2.195505 -0.524602 H -3.805477 -1.060900 -1.708446 O -1.320396 2.220695 1.343651 H 1.727084 3.773171 -0.352803 C 3.402718 1.755807 -0.284722 H 3.854187 2.711835 -0.538894 C 4.191870 0.602058 -0.323000 H 5.240561 0.648124 -0.600384 C 3.632766 -0.643975 -0.041381 O 4.387930 -1.777618 -0.119493 H 3.796464 -2.525122 0.077448 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -961.717342216 Predicted Change= -4.843451D-10 Zero-point correction (ZPE)= -961.3662 0.35105 Internal Energy (U)= -961.3482 0.36911 Enthalpy (H)= -961.3472 0.37005 Gibbs Free Energy (G)= -961.4124 0.30487 ------------------------------------------------------------------------------ Frequencies -- -138.3989 22.7856 38.0975

5.1.10 TSb→ba Supporting Information: CO-mAnsa-pAnsa-015-acerogenin-L-TSmAnsa.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -961.710012939 Predicted Change= -2.136834D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00114 || 0.00180 [ YES ] 0.00114 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.424332 -1.791768 -1.160408 H 1.714526 -1.622574 -2.193990 C 0.082642 -1.974030 -0.857679 H -0.674269 -1.933400 -1.634759 C -0.304610 -2.094742 0.477615 O -1.661349 -2.000515 0.808206 C -2.181846 -0.750867 0.441993 C 0.645634 -2.188166 1.488400 H 0.324220 -2.319528 2.517214 C 1.995819 -2.010004 1.163771 H 2.736919 -2.012822 1.960231 C 2.394071 -1.728235 -0.148038 C -1.540431 0.440453 0.761502 H -0.641493 0.395916 1.367852 C -2.017185 1.662823 0.278223 C -1.363188 2.979658 0.653840 H -1.881301 3.774208 0.108072 C 0.185969 3.196040 0.468015 H 0.608527 3.512807 1.425480 H 0.320891 4.039844 -0.220306 C 1.069999 2.087454 -0.132125 C 2.200299 1.539368 0.746422 H 1.843591 0.584815 1.154228 H 2.334360 2.202209 1.608960 C 3.581304 1.351153 0.071247 H 4.310026 1.191701 0.879047 H 3.859264 2.307088 -0.392908 C 3.780641 0.247128 -0.986624 H 3.032151 0.365742 -1.775895 H 4.758969 0.430662 -1.451572 C 3.779701 -1.221779 -0.484752 H 4.219607 -1.843916 -1.276401 H 4.441313 -1.317085 0.386554 O 0.897509 1.704514 -1.274856 H -1.577725 3.170615 1.713694 C -3.187520 1.644970 -0.494157 H -3.584152 2.579487 -0.883284 C -3.862598 0.456962 -0.777651

H -4.764331 0.452985 -1.382086 C -3.356438 -0.760039 -0.319497 O -3.974333 -1.933146 -0.634384 H -3.435266 -2.643843 -0.242442 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -961.710012939 Predicted Change= -2.136834D-09 Zero-point correction (ZPE)= -961.3589 0.35107 Internal Energy (U)= -961.3409 0.36909 Enthalpy (H)= -961.3399 0.37004 Gibbs Free Energy (G)= -961.4047 0.30525 ------------------------------------------------------------------------------ Frequencies -- -175.6205 30.3399 44.6730

5.1.11 TSb→bc Supporting Information: CO-pAnsa-mAnsa-015-acerogenin-L-TSpAnsa.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -961.711400359 Predicted Change= -6.837452D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00137 || 0.00180 [ YES ] 0.00137 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -2.019428 -1.832611 1.176550 H -2.489327 -1.587914 2.126572 C -0.663081 -2.152006 1.153860 H -0.072351 -2.151523 2.064782 C -0.034768 -2.353465 -0.074189 O 1.359703 -2.364020 -0.140149 C 1.928377 -1.084809 -0.202509 C -0.779050 -2.417768 -1.249359 H -0.278284 -2.628827 -2.189433 C -2.132503 -2.074095 -1.211047 H -2.692008 -2.020712 -2.142401 C -2.746454 -1.681096 -0.014362 C 1.273524 0.039658 -0.695163 H 0.260023 -0.056663 -1.062503 C 1.900557 1.291424 -0.718637 C 1.158393 2.498721 -1.264759 H 1.847241 3.108782 -1.862375 C 0.527778 3.446941 -0.202092 H 0.125459 4.323681 -0.727915 H 1.304812 3.783720 0.490827 C -0.575884 2.811475 0.636092 C -1.981162 2.605012 0.040873 H -2.095621 3.105237 -0.927925 H -2.677189 3.081574 0.743924 C -2.288787 1.094414 -0.055948 H -1.749615 0.612700 0.761596 H -1.857686 0.704546 -0.985122 C -3.769749 0.685111 0.033766 H -4.174775 1.070208 0.977933 H -4.344389 1.171586 -0.764457 C -4.029261 -0.876686 -0.035313 H -4.675005 -1.162368 0.803069 H -4.586998 -1.107697 -0.949607 O -0.355972 2.448035 1.777264 H 0.375120 2.162335 -1.955849 C 3.216678 1.376460 -0.247899 H 3.735601 2.332144 -0.260293 C 3.883822 0.249609 0.236939 H 4.903608 0.314622 0.603545 C 3.245740 -0.991129 0.267883 O 3.894976 -2.088747 0.749576 H 3.263275 -2.828521 0.713983 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm


S25

S25

============================================================================== SCF Energy= -961.711400359 Predicted Change= -6.837452D-09 Zero-point correction (ZPE)= -961.3602 0.35116 Internal Energy (U)= -961.3421 0.36925 Enthalpy (H)= -961.3412 0.37019 Gibbs Free Energy (G)= -961.4063 0.30504 ------------------------------------------------------------------------------ Frequencies -- -125.2003 29.8376 46.6311

5.1.12 TSc→ca Supporting Information: pAnsa-CO-mAnsa-Acerogenin-L-f-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -961.719777164 Predicted Change= -2.242244D-09 ============================================================================== Optimization completed on the basis of negligible forces. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00239 || 0.00180 [ NO ] 0.00239 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.462290 -2.001599 -1.249490 H 1.844305 -1.880499 -2.260478 C 0.086720 -2.106043 -1.048335 H -0.606637 -2.057870 -1.882647 C -0.407053 -2.179495 0.252937 O -1.777685 -2.050507 0.484411 C -2.252499 -0.746403 0.311738 C 0.460362 -2.287286 1.337489 H 0.053714 -2.384304 2.339467 C 1.833930 -2.179615 1.118148 H 2.508194 -2.198209 1.971319 C 2.350719 -1.956599 -0.167147 C -1.493315 0.388351 0.573126 H -0.491375 0.269301 0.967524 C -1.998442 1.669310 0.314840 C -1.126536 2.897410 0.497396 H -1.762446 3.785811 0.423593 C 0.026841 3.039204 -0.553270 H 0.151425 4.104120 -0.780059 H -0.253988 2.529731 -1.480459 C 1.404082 2.577767 -0.057127 C 1.956752 1.242436 -0.557021 H 1.559382 1.032641 -1.555292 H 1.485759 0.492659 0.091067 C 3.497026 1.108167 -0.504268 H 3.887435 1.999969 -0.001094 H 3.892280 1.128687 -1.528596 C 4.079870 -0.114953 0.234164 H 5.170415 0.011885 0.262703 H 3.746642 -0.090692 1.280715 C 3.791875 -1.526927 -0.344564 H 4.062295 -1.551123 -1.408131 H 4.459160 -2.236940 0.162569 O 2.012299 3.257200 0.750912 H -0.686091 2.924758 1.502088 C -3.311428 1.769112 -0.162431 H -3.733823 2.749379 -0.369289 C -4.094455 0.633507 -0.386029 H -5.111232 0.715795 -0.757507 C -3.567581 -0.638033 -0.163147 O -4.312643 -1.751143 -0.414912 H -3.746137 -2.519377 -0.222832 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -961.719777164 Predicted Change= -2.242244D-09 Zero-point correction (ZPE)= -961.3688 0.35089 Internal Energy (U)= -961.3508 0.36896 Enthalpy (H)= -961.3498 0.36991 Gibbs Free Energy (G)= -961.4155 0.30420

------------------------------------------------------------------------------ Frequencies -- -65.6983 17.7110 31.5515

5.1.13 TSc→cb Supporting Information: pAnsa-mAnsa-CO-015-acerogenin-L-TSmAnsa.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -961.710220512 Predicted Change= -1.086547D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00067 || 0.00180 [ YES ] 0.00067 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.359722 -2.147427 -1.058519 H 1.619023 -2.269729 -2.107773 C 0.031787 -2.298890 -0.661401 H -0.748422 -2.519305 -1.384266 C -0.309414 -2.048120 0.666709 O -1.659664 -1.889676 1.015914 C -2.148438 -0.679074 0.498083 C 0.673215 -1.811288 1.623425 H 0.386866 -1.658130 2.659285 C 1.994924 -1.656807 1.208103 H 2.748081 -1.377832 1.939973 C 2.342811 -1.738338 -0.147376 C -1.532255 0.542265 0.757315 H -0.694912 0.565169 1.445841 C -1.947691 1.702853 0.094165 C -1.318640 3.066745 0.337778 H -1.637876 3.720745 -0.480372 C 0.236403 3.235916 0.522109 H 0.431232 3.659211 1.510682 H 0.580065 3.973627 -0.216081 C 1.194595 2.043161 0.414877 C 1.434373 1.392342 -0.943588 H 0.940115 1.984537 -1.723494 H 0.918128 0.427273 -0.923742 C 2.922781 1.199736 -1.344595 H 3.385736 2.195076 -1.388418 H 2.928413 0.827212 -2.378907 C 3.843469 0.304144 -0.483459 H 4.877398 0.543439 -0.768254 H 3.735287 0.586245 0.567334 C 3.686041 -1.233226 -0.623956 H 3.840323 -1.522444 -1.672052 H 4.496062 -1.702231 -0.048885 O 1.787656 1.665268 1.413583 H -1.778288 3.493658 1.239036 C -3.041053 1.597247 -0.780750 H -3.388755 2.482738 -1.307736 C -3.700598 0.387325 -0.994289 H -4.541438 0.317356 -1.677407 C -3.245573 -0.772506 -0.364981 O -3.829113 -1.976889 -0.619451 H -3.346826 -2.632585 -0.083016 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -961.710220512 Predicted Change= -1.086547D-09 Zero-point correction (ZPE)= -961.3587 0.35143 Internal Energy (U)= -961.3409 0.36929 Enthalpy (H)= -961.3399 0.37024 Gibbs Free Energy (G)= -961.4039 0.30626 ------------------------------------------------------------------------------ Frequencies -- -154.2800 34.4329 63.1273


S26

S26

5.1.14 Intab Supporting Information: mAnsa-CO-pAnsa-020-Acerogenin-L.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -961.727642425 Predicted Change= -3.760965D-08 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00149 || 0.00180 [ YES ] 0.00149 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.723447 -2.014064 1.167509 H -2.328107 -1.980920 2.070628 C -0.344140 -2.178617 1.280170 H 0.137264 -2.258543 2.249909 C 0.437972 -2.133512 0.128617 O 1.823776 -2.025591 0.247007 C 2.282381 -0.706449 0.180034 C -0.151784 -2.067311 -1.131387 H 0.476273 -2.065024 -2.017174 C -1.535791 -1.915281 -1.226681 H -1.994529 -1.818108 -2.208383 C -2.332647 -1.807715 -0.079205 C 1.480754 0.403079 0.417391 H 0.448722 0.261281 0.710765 C 1.989040 1.701703 0.279601 C 1.067190 2.892396 0.470729 H 0.698651 2.934305 1.503456 C -0.163668 2.883199 -0.464063 H 0.106418 2.527804 -1.465684 H -0.528064 3.914205 -0.599771 C -1.383211 2.108682 0.054165 C -2.322559 1.560764 -1.013510 H -1.820036 0.679371 -1.435380 H -2.352872 2.288812 -1.837081 C -3.764383 1.236589 -0.578247 H -4.351130 1.071977 -1.493227 H -4.181883 2.138900 -0.112569 C -4.029853 0.061490 0.386436 H -3.458813 0.214157 1.307292 H -5.090636 0.126022 0.663532 C -3.782554 -1.376733 -0.147893 H -4.391128 -2.064134 0.454599 H -4.153717 -1.460110 -1.178007 O -1.592068 1.971094 1.247132 H 1.635855 3.812772 0.298658 C 3.336122 1.846589 -0.067144 H 3.759156 2.841524 -0.183303 C 4.155511 0.731710 -0.274479 H 5.200409 0.845438 -0.546645 C 3.634862 -0.555842 -0.162596 O 4.422384 -1.645826 -0.394690 H 3.856670 -2.431199 -0.293911 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -961.727642425 Predicted Change= -3.760965D-08 Zero-point correction (ZPE)= -961.3764 0.35122 Internal Energy (U)= -961.3577 0.36985 Enthalpy (H)= -961.3568 0.37080 Gibbs Free Energy (G)= -961.4227 0.30489 ------------------------------------------------------------------------------ Frequencies -- 30.5439 49.9491 61.5190

5.1.15 Intac Supporting Information: mAnsa-pAnsa-CO-020-Acerogenin-L.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ==============================================================================

# b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -961.727642440 Predicted Change= -1.624026D-08 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00097 || 0.00180 [ YES ] 0.00097 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.723484 -2.013608 1.167756 H -2.327888 -1.980112 2.071033 C -0.344170 -2.178393 1.280167 H 0.137371 -2.258134 2.249852 C 0.437741 -2.133557 0.128487 O 1.823587 -2.025652 0.246624 C 2.282338 -0.706512 0.179875 C -0.152235 -2.067523 -1.131434 H 0.475683 -2.065402 -2.017320 C -1.536233 -1.915384 -1.226480 H -1.995156 -1.818264 -2.208100 C -2.332888 -1.807485 -0.078856 C 1.480828 0.403126 0.417191 H 0.448743 0.261484 0.710412 C 1.989260 1.701705 0.279579 C 1.067408 2.892451 0.470578 H 0.699129 2.934548 1.503396 C -0.163482 2.883019 -0.464054 H 0.106623 2.527438 -1.465639 H -0.527900 3.913967 -0.600176 C -1.382964 2.108567 0.054094 C -2.322301 1.560648 -1.013601 H -1.819960 0.678794 -1.434807 H -2.352317 2.288177 -1.837577 C -3.764257 1.236848 -0.578408 H -4.350941 1.072262 -1.493434 H -4.181670 2.139254 -0.112818 C -4.030017 0.061922 0.386400 H -3.459155 0.214714 1.307352 H -5.090865 0.126628 0.663255 C -3.782777 -1.376394 -0.147555 H -4.391431 -2.063644 0.455046 H -4.153895 -1.460010 -1.177669 O -1.591872 1.970697 1.247035 H 1.636064 3.812794 0.298251 C 3.336413 1.846477 -0.066942 H 3.759626 2.841346 -0.183011 C 4.155677 0.731504 -0.274224 H 5.200635 0.845129 -0.546211 C 3.634865 -0.556010 -0.162545 O 4.422339 -1.646042 -0.394647 H 3.856547 -2.431390 -0.294105 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -961.727642440 Predicted Change= -1.624026D-08 Zero-point correction (ZPE)= -961.3764 0.35122 Internal Energy (U)= -961.3577 0.36985 Enthalpy (H)= -961.3568 0.37079 Gibbs Free Energy (G)= -961.4227 0.30489 ------------------------------------------------------------------------------ Frequencies -- 30.5149 49.9467 61.5010

5.1.16 Intba Supporting Information: CO-mAnsa-pAnsa-020-acerogenin-L.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -961.727642456 Predicted Change= -1.629790D-08


S27

S27

============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00149 || 0.00180 [ YES ] 0.00149 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.723369 -2.013714 1.167454 H -2.328019 -1.980326 2.070568 C -0.344092 -2.178489 1.280198 H 0.137218 -2.258293 2.249993 C 0.438109 -2.133517 0.128709 O 1.823922 -2.025498 0.247235 C 2.282515 -0.706335 0.180156 C -0.151558 -2.067377 -1.131342 H 0.476564 -2.065120 -2.017083 C -1.535548 -1.915285 -1.226723 H -1.994205 -1.818106 -2.208463 C -2.332477 -1.807488 -0.079308 C 1.480892 0.403173 0.417584 H 0.448922 0.261381 0.711120 C 1.989057 1.701828 0.279613 C 1.067027 2.892459 0.470522 H 0.698758 2.934583 1.503351 C -0.163847 2.882739 -0.464071 H 0.106145 2.526732 -1.465548 H -0.528321 3.913598 -0.600644 C -1.383320 2.108310 0.054335 C -2.322936 1.560799 -1.013366 H -1.820641 0.679269 -1.435266 H -2.353270 2.288856 -1.836890 C -3.764727 1.236672 -0.577966 H -4.351574 1.072303 -1.492931 H -4.182168 2.138880 -0.112017 C -4.030189 0.061316 0.386435 H -3.459346 0.213876 1.307430 H -5.091043 0.125624 0.663288 C -3.782439 -1.376638 -0.148300 H -4.391196 -2.064478 0.453524 H -4.153107 -1.459616 -1.178629 O -1.591988 1.970214 1.247262 H 1.635560 3.812855 0.298105 C 3.336088 1.846778 -0.067245 H 3.759094 2.841704 -0.183594 C 4.155525 0.731911 -0.274571 H 5.200394 0.845712 -0.546826 C 3.634954 -0.555659 -0.162626 O 4.422495 -1.645630 -0.394800 H 3.856815 -2.431025 -0.293988 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -961.727642456 Predicted Change= -1.629790D-08 Zero-point correction (ZPE)= -961.3764 0.35122 Internal Energy (U)= -961.3577 0.36985 Enthalpy (H)= -961.3568 0.37079 Gibbs Free Energy (G)= -961.4227 0.30489 ------------------------------------------------------------------------------ Frequencies -- 30.5392 49.9735 61.4942

5.1.17 Intbc Supporting Information: CO-pAnsa-mAnsa-020-acerogenin-L.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -961.724542490 Predicted Change= -8.521162D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00126 || 0.00180 [ YES ] 0.00126 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z

------------------------------------------------------------------------------ C -1.707506 -1.516773 1.231189 H -2.097717 -1.148534 2.176163 C -0.346880 -1.790996 1.121045 H 0.325301 -1.619027 1.955962 C 0.168988 -2.198984 -0.107745 O 1.555601 -2.236513 -0.294614 C 2.118119 -0.955810 -0.304448 C -0.675523 -2.450322 -1.186193 H -0.254801 -2.796074 -2.125574 C -2.037886 -2.166887 -1.060288 H -2.690075 -2.308744 -1.919410 C -2.563291 -1.634295 0.126016 C 1.458854 0.146038 -0.834991 H 0.497210 -0.000913 -1.311382 C 1.996098 1.431690 -0.733184 C 1.172154 2.615415 -1.200155 H 1.832446 3.408008 -1.572785 C 0.279063 3.246374 -0.097305 H -0.227409 4.121549 -0.533386 H 0.902380 3.602751 0.728464 C -0.808792 2.369799 0.530892 C -1.849677 1.707523 -0.377924 H -1.406438 0.761895 -0.714557 H -1.995285 2.308435 -1.285791 C -3.191807 1.425603 0.323757 H -3.743830 2.370724 0.400625 H -2.979793 1.121836 1.353838 C -4.082601 0.370214 -0.376544 H -5.134881 0.666678 -0.281067 H -3.870978 0.357438 -1.454722 C -3.968112 -1.076329 0.179690 H -4.323155 -1.078174 1.218012 H -4.654010 -1.717855 -0.388704 O -0.854729 2.227288 1.739578 H 0.545636 2.314531 -2.049346 C 3.258864 1.568260 -0.141301 H 3.710503 2.553445 -0.051828 C 3.951311 0.457730 0.346845 H 4.928457 0.563913 0.807855 C 3.380169 -0.815842 0.285921 O 4.034654 -1.892909 0.804410 H 3.442954 -2.659265 0.700975 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -961.724542490 Predicted Change= -8.521162D-09 Zero-point correction (ZPE)= -961.3732 0.35132 Internal Energy (U)= -961.3545 0.37001 Enthalpy (H)= -961.3535 0.37096 Gibbs Free Energy (G)= -961.4200 0.30449 ------------------------------------------------------------------------------ Frequencies -- 28.1169 39.5593 57.3746

5.1.18 Intca Supporting Information: pAnsa-mAnsa-CO-020-acerogenin-L.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -961.722066348 Predicted Change= -3.327030D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00206 || 0.00180 [ NO ] 0.00206 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.805904 -2.182679 -1.143083 H 2.445562 -2.293353 -2.015879 C 0.429681 -2.399759 -1.275358 H -0.011330 -2.656354 -2.233816 C -0.394012 -2.175121 -0.177744 O -1.780756 -2.098272 -0.356021 C -2.235611 -0.776779 -0.294921


S28

S28

C 0.148584 -1.873734 1.071632 H -0.511810 -1.721728 1.919806 C 1.517376 -1.662581 1.186237 H 1.925088 -1.360690 2.146723 C 2.359339 -1.740893 0.065168 C -1.473474 0.298769 -0.732358 H -0.511156 0.104725 -1.188087 C -1.908765 1.615451 -0.562626 C -0.984521 2.754473 -0.946766 H -0.488304 2.524937 -1.898761 C 0.086389 3.107258 0.122172 H -0.398610 3.338875 1.075295 H 0.604527 4.019489 -0.214436 C 1.188198 2.085012 0.432344 C 2.029297 1.539232 -0.722885 H 1.944662 2.221462 -1.579235 H 1.566159 0.599109 -1.045737 C 3.529570 1.308047 -0.421687 H 3.950312 2.259524 -0.069937 H 4.022310 1.101331 -1.382567 C 3.946651 0.219262 0.591283 H 5.013290 0.378020 0.801177 H 3.417564 0.388648 1.532704 C 3.793482 -1.261544 0.158627 H 4.297091 -1.417240 -0.804879 H 4.339006 -1.874057 0.890457 O 1.410796 1.767612 1.588176 H -1.574595 3.661749 -1.123026 C -3.172719 1.818036 0.005574 H -3.546197 2.829442 0.147275 C -3.967236 0.738897 0.403035 H -4.945936 0.896260 0.845801 C -3.500428 -0.570603 0.271349 O -4.255096 -1.621709 0.699772 H -3.723428 -2.425655 0.561740 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -961.722066348 Predicted Change= -3.327030D-08 Zero-point correction (ZPE)= -961.3707 0.35131 Internal Energy (U)= -961.3521 0.36992 Enthalpy (H)= -961.3512 0.37086 Gibbs Free Energy (G)= -961.4171 0.30495 ------------------------------------------------------------------------------ Frequencies -- 27.8069 54.5444 59.4035

5.1.19 Intcb Supporting Information: pAnsa-CO-mAnsa-Acerogenin-L-i-GS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -961.724542478 Predicted Change= -5.288800D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00078 || 0.00180 [ YES ] 0.00078 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.707613 -1.516658 1.231194 H -2.097802 -1.148326 2.176138 C -0.346989 -1.790941 1.121057 H 0.325197 -1.618945 1.955965 C 0.168875 -2.198923 -0.107724 O 1.555485 -2.236455 -0.294564 C 2.118064 -0.955778 -0.304449 C -0.675643 -2.450249 -1.186187 H -0.254913 -2.796014 -2.125553 C -2.037986 -2.166767 -1.060293 H -2.690164 -2.308573 -1.919428 C -2.563388 -1.634159 0.126015 C 1.458831 0.146152 -0.834880 H 0.497122 -0.000681 -1.311169 C 1.996204 1.431755 -0.733096

C 1.172296 2.615550 -1.199930 H 1.832596 3.408231 -1.572355 C 0.279080 3.246296 -0.097052 H -0.227467 4.121451 -0.533085 H 0.902321 3.602652 0.728788 C -0.808650 2.369476 0.530976 C -1.849582 1.707446 -0.377948 H -1.406518 0.761716 -0.714510 H -1.994947 2.308367 -1.285864 C -3.191864 1.425819 0.323555 H -3.743808 2.371005 0.400158 H -2.980051 1.122214 1.353738 C -4.082684 0.370388 -0.376643 H -5.134948 0.666862 -0.281086 H -3.871155 0.357567 -1.454842 C -3.968183 -1.076124 0.179670 H -4.323177 -1.077895 1.218007 H -4.654108 -1.717662 -0.388660 O -0.854490 2.226589 1.739631 H 0.545840 2.314806 -2.049219 C 3.259041 1.568205 -0.141341 H 3.710782 2.553347 -0.051891 C 3.951444 0.457593 0.346688 H 4.928648 0.563690 0.807598 C 3.380188 -0.815919 0.285795 O 4.034632 -1.893062 0.804191 H 3.442877 -2.659370 0.700761 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -961.724542478 Predicted Change= -5.288800D-09 Zero-point correction (ZPE)= -961.3732 0.35132 Internal Energy (U)= -961.3545 0.37001 Enthalpy (H)= -961.3535 0.37096 Gibbs Free Energy (G)= -961.4200 0.30448 ------------------------------------------------------------------------------ Frequencies -- 28.1060 39.5840 57.3586

5.1.20 TSab→abc Supporting Information: mAnsa-CO-pAnsa-025-Acerogenin-L-TSpAnsa.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -961.715281104 Predicted Change= -7.287930D-09 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00318 || 0.00180 [ NO ] 0.00318 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.771038 -2.014420 1.259658 H -2.358124 -2.005334 2.174835 C -0.393611 -2.220043 1.337703 H 0.102246 -2.359744 2.293361 C 0.368377 -2.140378 0.175255 O 1.762116 -2.080182 0.266916 C 2.247053 -0.769636 0.194995 C -0.242986 -1.994790 -1.067850 H 0.368218 -1.968908 -1.965154 C -1.623391 -1.810068 -1.130100 H -2.096622 -1.673629 -2.099439 C -2.399334 -1.742833 0.036485 C 1.513593 0.333789 0.608498 H 0.534531 0.192566 1.045352 C 2.012334 1.632169 0.446842 C 1.139364 2.815107 0.822667 H 0.759962 2.697212 1.844399 C -0.071960 3.025985 -0.113120 H 0.238938 2.975709 -1.163434 H -0.467403 4.043867 0.033942 C -1.271201 2.088756 0.124340 C -2.229197 1.996307 -1.062705


S29

S29

H -1.594968 1.774168 -1.931207 H -2.544092 3.037804 -1.232961 C -3.484299 1.066722 -1.107753 H -3.320327 0.354314 -1.923956 H -4.314993 1.693107 -1.451580 C -3.975562 0.269110 0.135952 H -3.457100 0.597314 1.036941 H -5.041771 0.482544 0.282838 C -3.835974 -1.272735 0.000279 H -4.396338 -1.740147 0.819813 H -4.318436 -1.595192 -0.932500 O -1.440167 1.545915 1.200983 H 1.744237 3.729046 0.809072 C 3.292412 1.781652 -0.098831 H 3.710100 2.776844 -0.232957 C 4.051110 0.669924 -0.480359 H 5.043493 0.786287 -0.905256 C 3.530651 -0.617374 -0.348995 O 4.250870 -1.702955 -0.754402 H 3.687847 -2.483518 -0.607836 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -961.715281104 Predicted Change= -7.287930D-09 Zero-point correction (ZPE)= -961.3641 0.35110 Internal Energy (U)= -961.3461 0.36915 Enthalpy (H)= -961.3451 0.37009 Gibbs Free Energy (G)= -961.4102 0.30498 ------------------------------------------------------------------------------ Frequencies -- -192.4980 20.1639 43.6154

5.1.21 TSac→acb Supporting Information: mAnsa-pAnsa-CO-025-Acerogenin-L-TSco.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -961.719777235 Predicted Change= -5.235380D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00173 || 0.00180 [ YES ] 0.00173 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.833768 -2.180215 1.118034 H -2.508180 -2.199109 1.971081 C -0.460226 -2.287809 1.337584 H -0.053739 -2.385052 2.339605 C 0.407361 -2.179613 0.253213 O 1.777934 -2.050441 0.484980 C 2.252553 -0.746293 0.312069 C -0.086196 -2.105874 -1.048127 H 0.607297 -2.057390 -1.882309 C -1.461737 -2.001511 -1.249490 H -1.843590 -1.880185 -2.260512 C -2.350356 -1.956883 -0.167285 C 1.493344 0.388352 0.573886 H 0.491631 0.269144 0.968828 C 1.998137 1.669377 0.315308 C 1.126095 2.897322 0.498188 H 0.685320 2.924051 1.502747 C -0.026959 3.039556 -0.552810 H 0.254106 2.530287 -1.480042 H -0.151403 4.104538 -0.779330 C -1.404332 2.577970 -0.057169 C -1.956524 1.242376 -0.556911 H -1.485534 0.492767 0.091379 H -1.558829 1.032557 -1.555046 C -3.496795 1.107819 -0.504630 H -3.891722 1.128077 -1.529089 H -3.887524 1.999632 -0.001728 C -4.079638 -0.115295 0.233806

H -3.746499 -0.090970 1.280385 H -5.170196 0.011465 0.262244 C -3.791505 -1.527272 -0.344851 H -4.458807 -2.237298 0.162241 H -4.061821 -1.551507 -1.408445 O -2.013090 3.257568 0.750325 H 1.761928 3.785836 0.425086 C 3.310862 1.769367 -0.162663 H 3.733006 2.749696 -0.369740 C 4.093937 0.633882 -0.386667 H 5.110511 0.716320 -0.758668 C 3.567356 -0.637739 -0.163520 O 4.312436 -1.750740 -0.415699 H 3.746137 -2.519050 -0.223303 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -961.719777235 Predicted Change= -5.235380D-09 Zero-point correction (ZPE)= -961.3688 0.35089 Internal Energy (U)= -961.3508 0.36896 Enthalpy (H)= -961.3498 0.36991 Gibbs Free Energy (G)= -961.4155 0.30421 ------------------------------------------------------------------------------ Frequencies -- -65.6817 17.8385 31.5882

5.1.22 TSba→bac Supporting Information: CO-mAnsa-pAnsa-025-acerogenin-L-TS-pAnsa.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -961.717342230 Predicted Change= -8.402940D-11 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00032 || 0.00180 [ YES ] 0.00032 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.877387 -1.873860 1.002864 H -2.580498 -1.780585 1.825744 C -0.523053 -2.046407 1.295046 H -0.168468 -2.069505 2.320799 C 0.397706 -2.081290 0.252093 O 1.760806 -1.986510 0.535437 C 2.275361 -0.705536 0.303410 C -0.031137 -2.078768 -1.074092 H 0.700765 -2.130151 -1.874526 C -1.386167 -1.909310 -1.348247 H -1.714614 -1.849533 -2.383775 C -2.323315 -1.733273 -0.318573 C 1.506272 0.448680 0.381772 H 0.470443 0.370800 0.684758 C 2.048473 1.700004 0.064609 C 1.167129 2.937008 0.079919 H 0.922094 3.219891 1.111514 C -0.165591 2.778863 -0.686855 H -0.026221 2.209820 -1.614180 H -0.528465 3.771495 -0.997550 C -1.315781 2.176313 0.126891 C -2.456666 1.536742 -0.672253 H -2.026853 0.626480 -1.106676 H -2.669064 2.183191 -1.534859 C -3.729975 1.253779 0.157892 H -4.514494 1.930875 -0.196910 H -3.507054 1.566132 1.182250 C -4.338086 -0.189417 0.218430 H -4.327822 -0.522580 1.262829 H -5.400723 -0.121047 -0.044378 C -3.750713 -1.329006 -0.645375 H -4.417626 -2.195384 -0.524463 H -3.805660 -1.060803 -1.708335 O -1.320287 2.221111 1.343619 H 1.727245 3.773095 -0.353109 C 3.402852 1.755712 -0.284615


S30

S30

H 3.854401 2.711726 -0.538693 C 4.191968 0.601934 -0.322772 H 5.240708 0.647967 -0.599974 C 3.632775 -0.644081 -0.041256 O 4.387920 -1.777747 -0.119232 H 3.796403 -2.525235 0.077612 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -961.717342230 Predicted Change= -8.402940D-11 Zero-point correction (ZPE)= -961.3662 0.35105 Internal Energy (U)= -961.3482 0.36911 Enthalpy (H)= -961.3472 0.37005 Gibbs Free Energy (G)= -961.4124 0.30487 ------------------------------------------------------------------------------ Frequencies -- -138.3943 22.7994 38.0974

5.1.23 TSbc→bca Supporting Information: CO-pAnsa-mAnsa-025-acerogenin-L-TSmAnsa.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -961.716024873 Predicted Change= -1.801225D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00058 || 0.00180 [ YES ] 0.00058 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.740503 -1.588222 -1.168754 H 2.042831 -1.364344 -2.188406 C 0.404649 -1.870871 -0.905246 H -0.336503 -1.848229 -1.698029 C 0.003638 -2.098201 0.410168 O -1.358917 -2.183242 0.713096 C -2.035078 -0.990969 0.422394 C 0.939806 -2.160671 1.439575 H 0.608542 -2.375618 2.451039 C 2.277788 -1.871810 1.157386 H 3.001320 -1.865205 1.969911 C 2.686804 -1.518856 -0.136368 C -1.575054 0.245756 0.856217 H -0.688494 0.279000 1.482171 C -2.219803 1.426126 0.470487 C -1.729682 2.772991 0.965467 H -2.446314 3.534947 0.644215 C -0.285775 3.264797 0.569534 H 0.254403 3.541568 1.480284 H -0.391833 4.181994 -0.021763 C 0.600593 2.355643 -0.294663 C 1.875885 1.795360 0.340558 H 1.569733 0.882502 0.873723 H 2.234826 2.481282 1.118912 C 3.005503 1.470972 -0.651731 H 3.434996 2.417842 -1.001959 H 2.566645 0.997764 -1.535607 C 4.128117 0.587478 -0.049904 H 5.106092 0.951208 -0.389344 H 4.132050 0.695474 1.043340 C 4.050666 -0.924479 -0.403216 H 4.297253 -1.049257 -1.465048 H 4.826247 -1.454413 0.164709 O 0.302634 2.113648 -1.448973 H -1.775603 2.769909 2.061775 C -3.367069 1.312749 -0.325685 H -3.890345 2.212438 -0.639529 C -3.858838 0.069930 -0.728445 H -4.746126 -0.009662 -1.348755 C -3.188105 -1.098453 -0.365019 O -3.633228 -2.315223 -0.787171 H -3.010911 -2.976273 -0.433788 ------------------------------------------------------------------------------

Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -961.716024873 Predicted Change= -1.801225D-09 Zero-point correction (ZPE)= -961.3649 0.35104 Internal Energy (U)= -961.3468 0.36912 Enthalpy (H)= -961.3459 0.37007 Gibbs Free Energy (G)= -961.4109 0.30506 ------------------------------------------------------------------------------ Frequencies -- -150.3757 28.7610 50.9208

5.1.24 TSca→cab Supporting Information: pAnsa-mAnsa-CO-025-acerogenin-L-TSco.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -961.718762762 Predicted Change= -2.203388D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00124 || 0.00180 [ YES ] 0.00124 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.599501 -2.326161 1.122918 H -2.238131 -2.396265 2.000186 C -0.211458 -2.377822 1.284648 H 0.238100 -2.472733 2.268419 C 0.604958 -2.202962 0.172238 O 1.975081 -1.990353 0.347094 C 2.332007 -0.641209 0.250701 C 0.054853 -2.117082 -1.107810 H 0.712191 -2.015780 -1.966214 C -1.329062 -2.078095 -1.252471 H -1.756014 -1.961149 -2.246116 C -2.177278 -2.105020 -0.133114 C 1.465090 0.397024 0.564108 H 0.478193 0.156515 0.933485 C 1.834217 1.734457 0.380231 C 0.818317 2.836152 0.625087 H 0.337832 2.688000 1.600937 C -0.278562 2.978001 -0.487975 H 0.017270 2.371544 -1.354784 H -0.336391 4.016116 -0.826546 C -1.718337 2.587220 -0.126507 C -1.978372 1.165509 0.382261 H -1.520682 1.103604 1.379674 H -1.394104 0.478754 -0.237757 C -3.467180 0.755836 0.443073 H -4.058763 1.668422 0.313808 H -3.706428 0.373987 1.443833 C -3.922908 -0.279594 -0.608700 H -5.007599 -0.179775 -0.745163 H -3.474159 -0.034520 -1.581403 C -3.646510 -1.772019 -0.278492 H -4.174886 -2.032118 0.647687 H -4.093997 -2.382284 -1.074691 O -2.620640 3.391240 -0.274817 H 1.345131 3.793162 0.698415 C 3.131240 1.995240 -0.077263 H 3.454792 3.022455 -0.226789 C 4.024514 0.955196 -0.354151 H 5.029347 1.159683 -0.710787 C 3.630824 -0.375000 -0.205555 O 4.488427 -1.389997 -0.510381 H 4.004257 -2.222779 -0.370724 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -961.718762762 Predicted Change= -2.203388D-09 Zero-point correction (ZPE)= -961.3676 0.35113 Internal Energy (U)= -961.3496 0.36908 Enthalpy (H)= -961.3487 0.37003 Gibbs Free Energy (G)= -961.4132 0.30548


S31

S31

------------------------------------------------------------------------------ Frequencies -- -27.5974 27.5645 46.1447

5.1.25 TScb→cba Supporting Information: pAnsa-CO-mAnsa-Acerogenin-L-j-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -961.716024873 Predicted Change= -1.763127D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00057 || 0.00180 [ YES ] 0.00057 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.740502 -1.588224 -1.168754 H 2.042829 -1.364347 -2.188406 C 0.404649 -1.870874 -0.905245 H -0.336504 -1.848233 -1.698028 C 0.003638 -2.098202 0.410169 O -1.358917 -2.183242 0.713098 C -2.035078 -0.990969 0.422395 C 0.939806 -2.160670 1.439576 H 0.608543 -2.375616 2.451040 C 2.277788 -1.871809 1.157387 H 3.001321 -1.865202 1.969911 C 2.686803 -1.518857 -0.136368 C -1.575054 0.245755 0.856219 H -0.688496 0.278999 1.482174 C -2.219802 1.426126 0.470488 C -1.729683 2.772991 0.965468 H -2.446314 3.534946 0.644214 C -0.285775 3.264796 0.569536 H 0.254403 3.541565 1.480287 H -0.391833 4.181996 -0.021757 C 0.600592 2.355645 -0.294664 C 1.875883 1.795360 0.340557 H 1.569730 0.882502 0.873722 H 2.234825 2.481280 1.118912 C 3.005502 1.470972 -0.651731 H 3.434995 2.417842 -1.001959 H 2.566644 0.997764 -1.535607 C 4.128116 0.587477 -0.049905 H 5.106091 0.951208 -0.389345 H 4.132049 0.695473 1.043339 C 4.050664 -0.924479 -0.403217 H 4.297251 -1.049257 -1.465050 H 4.826246 -1.454413 0.164707 O 0.302634 2.113654 -1.448974 H -1.775605 2.769909 2.061775 C -3.367067 1.312748 -0.325686 H -3.890343 2.212437 -0.639531 C -3.858836 0.069929 -0.728447 H -4.746122 -0.009662 -1.348759 C -3.188104 -1.098453 -0.365020 O -3.633226 -2.315223 -0.787173 H -3.010910 -2.976273 -0.433789 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -961.716024873 Predicted Change= -1.763127D-09 Zero-point correction (ZPE)= -961.3649 0.35104 Internal Energy (U)= -961.3468 0.36912 Enthalpy (H)= -961.3459 0.37007 Gibbs Free Energy (G)= -961.4109 0.30506 ------------------------------------------------------------------------------ Frequencies -- -150.3763 28.7606 50.9205

5.1.26 ent-Acerogenin L Supporting Information: CO-mAnsa-pAnsa-030-acerogenin-L.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C19H20O3 C1[X(C19H20O3)] #Atoms= 42 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -961.730175294 Predicted Change= -6.872188D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.01058 || 0.00180 [ NO ] 0.01058 || 0.00180 [ NO ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -2.032577 -1.725745 1.266379 H -2.670483 -1.557486 2.130416 C -0.663423 -1.922652 1.460333 H -0.226032 -1.901252 2.453571 C 0.162334 -2.065402 0.350657 O 1.546625 -2.075599 0.521268 C 2.163777 -0.847373 0.263632 C -0.376392 -2.127525 -0.935647 H 0.284576 -2.271484 -1.785186 C -1.746128 -1.944326 -1.110497 H -2.159991 -1.958512 -2.116568 C -2.588100 -1.679850 -0.018052 C 1.547153 0.381019 0.464306 H 0.544471 0.407325 0.873536 C 2.206229 1.576124 0.141467 C 1.496494 2.908800 0.298596 H 1.248646 3.094921 1.351004 C 0.184526 3.020793 -0.513176 H 0.311188 2.607818 -1.520548 H -0.068997 4.084277 -0.642228 C -1.036369 2.396874 0.173875 C -2.032960 1.672920 -0.721707 H -1.503964 0.775908 -1.076892 H -2.203297 2.275039 -1.626424 C -3.360876 1.289342 -0.051289 H -3.976947 2.191808 0.040609 H -3.152793 0.969112 0.975099 C -4.148946 0.193365 -0.812900 H -5.216863 0.444357 -0.823998 H -3.836447 0.178066 -1.865975 C -4.020866 -1.238999 -0.226544 H -4.548425 -1.273367 0.734615 H -4.544733 -1.934913 -0.895534 O -1.183180 2.473135 1.381219 H 2.175287 3.709667 -0.014415 C 3.513646 1.491159 -0.350075 H 4.049771 2.400891 -0.609497 C 4.150155 0.258063 -0.520074 H 5.163808 0.196683 -0.904035 C 3.476922 -0.925486 -0.223926 O 4.078701 -2.133905 -0.416975 H 3.426456 -2.814526 -0.173790 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -961.730175294 Predicted Change= -6.872188D-08 Zero-point correction (ZPE)= -961.3790 0.35108 Internal Energy (U)= -961.3603 0.36984 Enthalpy (H)= -961.3593 0.37078 Gibbs Free Energy (G)= -961.4260 0.30417 ------------------------------------------------------------------------------ Frequencies -- 22.5657 54.7533 60.4018

5.2 Galeon

5.2.1 Galeon Supporting Information: 000-Galeon-New-GS.log ------------------------------------------------------------------------------


S32

S32

Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24995311 Predicted Change= -3.228649D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00186 || 0.00180 [ NO ] 0.00186 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.798545 -1.511452 0.849950 H -2.249597 -1.295166 1.812035 C -0.416337 -1.695966 0.761529 O 0.447145 -1.626723 1.805872 C -0.020286 -1.059545 3.026848 H -0.766981 -1.703438 3.509250 H -0.441736 -0.061363 2.858838 H 0.857499 -0.985425 3.670613 C 0.157152 -1.907933 -0.508212 O 1.538528 -1.917974 -0.648444 C 2.171853 -0.688913 -0.463974 C -0.650691 -2.032239 -1.630611 H -0.176587 -2.208064 -2.591630 C -2.035279 -1.867646 -1.523888 H -2.653937 -1.932587 -2.415379 C -2.614825 -1.550229 -0.290653 C 3.566811 -0.742088 -0.350978 O 4.231279 -1.932581 -0.411429 H 3.557057 -2.631376 -0.473819 C 4.267211 0.451776 -0.178336 H 5.349162 0.408203 -0.098153 C 3.585825 1.669056 -0.100056 H 4.154389 2.584148 0.048437 C 2.189815 1.726552 -0.197572 C 1.439879 3.039221 -0.031300 H 1.315552 3.257155 1.037999 C 0.042826 3.092419 -0.675370 H 0.060442 2.695911 -1.697771 H -0.268448 4.144563 -0.765250 C -1.070592 2.412863 0.131133 C -2.213590 1.809485 -0.680281 H -1.785991 0.941751 -1.203900 H -2.482330 2.511585 -1.483243 C -3.453915 1.392704 0.125217 H -4.051536 2.288825 0.331775 H -3.129459 1.022538 1.103325 C -4.333830 0.337874 -0.589332 H -4.215711 0.435709 -1.677170 H -5.392006 0.542519 -0.383368 C -4.067380 -1.137596 -0.182384 H -4.406266 -1.279335 0.851568 H -4.694146 -1.785522 -0.808623 O -1.035092 2.363652 1.348308 H 2.049829 3.852204 -0.443122 C 1.502258 0.525841 -0.399456 H 0.425751 0.521080 -0.490504 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24995311 Predicted Change= -3.228649D-08 Zero-point correction (ZPE)= -1075.8658 0.38406 Internal Energy (U)= -1075.8445 0.40537 Enthalpy (H)= -1075.8436 0.40631 Gibbs Free Energy (G)= -1075.9154 0.33447 ------------------------------------------------------------------------------ Frequencies -- 18.0306 43.9628 66.3638

5.2.2 TSa Supporting Information: 005-TS-C7-8-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc)

opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23867265 Predicted Change= -8.243988D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00049 || 0.00180 [ YES ] 0.00049 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.730141 -1.615556 0.717758 H -2.030460 -1.561012 1.758485 C -0.390853 -1.833910 0.397433 O 0.608103 -2.014545 1.300493 C 0.395528 -1.560768 2.637296 H -0.330295 -2.193685 3.163788 H 0.060465 -0.517480 2.641921 H 1.365335 -1.641497 3.130534 C -0.006299 -1.825187 -0.957273 O 1.349698 -1.831604 -1.275333 C 2.003589 -0.674635 -0.826609 C -0.963976 -1.732609 -1.958167 H -0.638129 -1.758942 -2.993828 C -2.307752 -1.531938 -1.622902 H -3.044641 -1.408125 -2.412574 C -2.690828 -1.406741 -0.283069 C 3.168377 -0.864888 -0.070509 O 3.632499 -2.115803 0.189863 H 2.939557 -2.732112 -0.109631 C 3.825896 0.256564 0.434146 H 4.723353 0.110935 1.027469 C 3.299417 1.532160 0.220502 H 3.808375 2.391061 0.651031 C 2.129803 1.727375 -0.522992 C 1.584304 3.117892 -0.779198 H 2.275274 3.841028 -0.335338 C 0.126953 3.471845 -0.294853 H -0.450518 3.840550 -1.147909 H 0.198736 4.305372 0.414632 C -0.691490 2.406125 0.447648 C -1.976240 1.916643 -0.223098 H -1.670743 1.087727 -0.878656 H -2.362133 2.693606 -0.895145 C -3.084411 1.445638 0.733750 H -3.523285 2.330456 1.211789 H -2.630797 0.862489 1.540948 C -4.202131 0.635683 0.029302 H -4.255417 0.933254 -1.026828 H -5.175220 0.897759 0.463540 C -4.064710 -0.911069 0.109385 H -4.282869 -1.227943 1.136967 H -4.836222 -1.360732 -0.528664 O -0.332749 1.986652 1.533558 H 1.612800 3.308430 -1.859626 C 1.505212 0.597782 -1.067709 H 0.604939 0.698825 -1.666594 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23867265 Predicted Change= -8.243988D-10 Zero-point correction (ZPE)= -1075.8548 0.38378 Internal Energy (U)= -1075.8341 0.40451 Enthalpy (H)= -1075.8332 0.40546 Gibbs Free Energy (G)= -1075.9035 0.33508 ------------------------------------------------------------------------------ Frequencies -- -151.5750 34.7501 47.2983

5.2.3 TSb Supporting Information: 005-TS-COout-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46


S33

S33

Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23890218 Predicted Change= -4.476318D-09 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00230 || 0.00180 [ NO ] 0.00230 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.992392 -2.254732 -0.523506 H 1.239082 -2.555355 -1.536449 C -0.343664 -2.093438 -0.146514 O -1.421326 -2.298136 -0.952382 C -1.191263 -2.675414 -2.302252 H -0.667150 -3.637635 -2.366377 H -0.614455 -1.911232 -2.838887 H -2.178966 -2.769065 -2.756166 C -0.628255 -1.603038 1.142611 O -1.913684 -1.140766 1.419117 C -2.177812 0.061865 0.748630 C 0.387869 -1.435951 2.071838 H 0.129501 -1.080727 3.065060 C 1.719038 -1.620471 1.689504 H 2.514283 -1.423509 2.403332 C 2.033859 -1.951945 0.367842 C -3.455397 0.200128 0.198399 O -4.385984 -0.783511 0.336025 H -3.927647 -1.540759 0.743628 C -3.749700 1.366656 -0.512498 H -4.742742 1.478557 -0.937083 C -2.768727 2.339362 -0.706162 H -3.012961 3.223599 -1.290925 C -1.476188 2.192853 -0.179223 C -0.398379 3.223644 -0.485179 H -0.117739 3.143545 -1.545767 C 0.876721 3.215680 0.382614 H 0.614907 3.063663 1.438171 H 1.322663 4.217532 0.350753 C 2.072458 2.279298 0.096372 C 2.001016 1.203202 -0.979780 H 1.614994 1.674232 -1.896112 H 1.227813 0.480901 -0.693637 C 3.344756 0.515229 -1.295723 H 4.068391 1.307015 -1.523062 H 3.218957 -0.058037 -2.225281 C 3.984548 -0.399081 -0.224391 H 3.916079 0.087630 0.752990 H 5.056434 -0.465768 -0.453996 C 3.460796 -1.855600 -0.124724 H 3.551353 -2.343150 -1.104463 H 4.126792 -2.401934 0.556670 O 3.085503 2.452376 0.752612 H -0.846059 4.221511 -0.390221 C -1.212640 1.050298 0.578859 H -0.238171 0.898005 1.024548 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23890218 Predicted Change= -4.476318D-09 Zero-point correction (ZPE)= -1075.8551 0.38373 Internal Energy (U)= -1075.8347 0.40418 Enthalpy (H)= -1075.8337 0.40513 Gibbs Free Energy (G)= -1075.9034 0.33542 ------------------------------------------------------------------------------ Frequencies -- -30.7471 19.7995 39.9809

5.2.4 TSc Supporting Information: 005-TS2-C11-12in-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23742562 Predicted Change= -2.752751D-09

============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00065 || 0.00180 [ YES ] 0.00065 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.708936 -1.544139 0.598323 H -2.238893 -1.322589 1.516212 C -0.328617 -1.756000 0.644069 O 0.428039 -1.709240 1.769261 C -0.159853 -1.175020 2.952583 H -0.950300 -1.831435 3.339254 H -0.562900 -0.171987 2.770825 H 0.649116 -1.121376 3.682821 C 0.369820 -1.942314 -0.565613 O 1.757951 -1.878709 -0.569409 C 2.268276 -0.590423 -0.395904 C -0.319092 -2.029107 -1.766141 H 0.248825 -2.168295 -2.681173 C -1.702253 -1.829830 -1.795605 H -2.225038 -1.840875 -2.748678 C -2.400170 -1.522507 -0.622382 C 3.645338 -0.511654 -0.156293 O 4.413626 -1.638323 -0.097451 H 3.811176 -2.397582 -0.183121 C 4.219661 0.747658 0.021005 H 5.288859 0.805951 0.201148 C 3.430504 1.899676 -0.017254 H 3.900830 2.867461 0.141395 C 2.049678 1.825208 -0.242098 C 1.177280 3.071181 -0.203349 H 1.060406 3.393602 0.839619 C -0.231615 2.932770 -0.804445 H -0.206416 2.446695 -1.788459 H -0.640777 3.938354 -0.988793 C -1.265580 2.237120 0.087291 C -2.530244 1.730271 -0.616673 H -2.211582 0.867711 -1.214766 H -2.826381 2.486840 -1.356060 C -3.697062 1.385885 0.338216 H -4.505424 2.098847 0.143555 H -3.346233 1.602468 1.351529 C -4.321783 -0.051616 0.339895 H -5.406054 0.049088 0.209757 H -4.201748 -0.481236 1.341717 C -3.860359 -1.103698 -0.690764 H -4.502822 -1.986622 -0.554996 H -4.069090 -0.745419 -1.707345 O -1.094539 2.120143 1.287440 H 1.696887 3.886997 -0.721378 C 1.492223 0.561685 -0.450213 H 0.433655 0.461577 -0.639678 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23742562 Predicted Change= -2.752751D-09 Zero-point correction (ZPE)= -1075.8534 0.38401 Internal Energy (U)= -1075.8328 0.40460 Enthalpy (H)= -1075.8318 0.40554 Gibbs Free Energy (G)= -1075.9019 0.33551 ------------------------------------------------------------------------------ Frequencies -- -120.4658 19.0215 50.8701

5.2.5 TSd Supporting Information: 005-TS-Ph-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.17860230 Predicted Change= -2.555559D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass?


S34

S34

Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00052 || 0.00180 [ YES ] 0.00052 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -0.196335 3.087979 -0.017103 H -0.285495 4.157132 -0.181097 C -1.366378 2.349462 0.295121 O -2.617039 2.890945 0.403203 C -2.761010 4.292552 0.248448 H -2.466518 4.622298 -0.757072 H -2.172430 4.843467 0.994042 H -3.821754 4.501616 0.399620 C -1.289098 0.949214 0.493007 O -2.421310 0.164906 0.802109 C -2.214486 -1.194546 0.485647 C -0.046933 0.370993 0.365295 H 0.103554 -0.678338 0.472780 C 1.071765 1.102608 0.087594 H 1.987847 0.573214 0.055957 C 1.061415 2.458449 -0.128616 C -2.826674 -1.664322 -0.680806 O -3.781613 -0.930628 -1.312018 H -3.868159 -0.098206 -0.810840 C -2.389916 -2.878411 -1.227104 H -2.876450 -3.250950 -2.123291 C -1.255673 -3.503677 -0.707711 H -0.839053 -4.357758 -1.237737 C -0.611489 -3.023101 0.445841 C 0.836018 -3.399717 0.766349 H 1.090672 -3.120358 1.794076 C 1.875318 -2.713470 -0.201382 H 1.382504 -2.398252 -1.128766 H 2.620623 -3.460181 -0.515876 C 2.705530 -1.526764 0.348528 C 3.516581 -0.692390 -0.690518 H 2.952834 -0.657468 -1.630521 H 4.398845 -1.312765 -0.910086 C 4.003848 0.750285 -0.275632 H 5.090931 0.765414 -0.407647 H 3.842290 0.874419 0.801323 C 3.428024 1.983130 -1.090926 H 2.958962 1.607749 -2.010077 H 4.292736 2.570877 -1.421179 C 2.439947 3.024715 -0.446725 H 2.896247 3.434104 0.467419 H 2.365611 3.869743 -1.144100 O 2.771135 -1.294326 1.539387 H 0.970661 -4.484533 0.685788 C -1.223052 -1.953542 1.116993 H -0.778253 -1.565092 2.028046 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.17860230 Predicted Change= -2.555559D-09 Zero-point correction (ZPE)= -1075.7945 0.38404 Internal Energy (U)= -1075.7741 0.40448 Enthalpy (H)= -1075.7731 0.40542 Gibbs Free Energy (G)= -1075.8423 0.33627 ------------------------------------------------------------------------------ Frequencies -- -148.1889 40.4129 49.3082

5.2.6 Inta Supporting Information: 010-GS-C7-8-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24756480 Predicted Change= -1.190469D-08 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00135 || 0.00180 [ YES ] 0.00135 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms)

Type X Y Z ------------------------------------------------------------------------------ C -1.689661 -1.537748 0.793784 H -2.055637 -1.304551 1.787187 C -0.329538 -1.786469 0.597791 O 0.617644 -1.776132 1.570256 C 0.259208 -1.266950 2.854386 H -0.464474 -1.923929 3.353944 H -0.147392 -0.252836 2.773648 H 1.185840 -1.250264 3.430118 C 0.136234 -2.002451 -0.714745 O 1.510527 -1.994955 -0.953448 C 2.063210 -0.723330 -0.759676 C -0.756686 -2.092028 -1.772932 H -0.364991 -2.280158 -2.768258 C -2.118554 -1.852667 -1.560625 H -2.804356 -1.870465 -2.403851 C -2.584108 -1.507028 -0.287657 C 3.296497 -0.664884 -0.099409 O 3.925617 -1.802403 0.301683 H 3.296660 -2.532018 0.154436 C 3.859891 0.588035 0.153599 H 4.817740 0.631496 0.662897 C 3.173544 1.754191 -0.193230 H 3.612372 2.718451 0.052891 C 1.928548 1.698851 -0.833009 C 1.095115 2.932265 -1.115006 H 1.742500 3.778099 -1.377203 C 0.219105 3.385200 0.087275 H -0.334527 4.287507 -0.214849 H 0.860476 3.653286 0.932306 C -0.802752 2.379593 0.621032 C -1.880058 1.841550 -0.323682 H -1.457702 0.936820 -0.778929 H -2.047188 2.545374 -1.149606 C -3.205397 1.489552 0.380166 H -3.743341 2.423728 0.585564 H -2.969763 1.059334 1.358868 C -4.129084 0.537231 -0.417268 H -3.973068 0.683446 -1.494909 H -5.174940 0.809255 -0.225164 C -3.986137 -0.973904 -0.085578 H -4.294179 -1.132455 0.955823 H -4.696125 -1.529820 -0.711389 O -0.760365 2.025205 1.787623 H 0.454332 2.753367 -1.987399 C 1.408563 0.438625 -1.144721 H 0.462746 0.356786 -1.668013 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24756480 Predicted Change= -1.190469D-08 Zero-point correction (ZPE)= -1075.8632 0.38436 Internal Energy (U)= -1075.8420 0.40553 Enthalpy (H)= -1075.8410 0.40647 Gibbs Free Energy (G)= -1075.9120 0.33550 ------------------------------------------------------------------------------ Frequencies -- 37.4391 55.5917 59.9447

5.2.7 Intb Supporting Information: 010-GS-COout-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23998119 Predicted Change= -1.005377D-08 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00178 || 0.00180 [ YES ] 0.00178 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.341888 -2.104337 0.566969 H -1.709688 -2.356652 1.556128


S35

S35

C 0.031858 -2.132812 0.304417 O 0.997158 -2.461320 1.205285 C 0.597981 -2.801976 2.524025 H -0.051876 -3.686700 2.532304 H 0.080168 -1.968070 3.015966 H 1.519300 -3.024525 3.064726 C 0.484923 -1.710398 -0.960160 O 1.836037 -1.424249 -1.136734 C 2.207425 -0.198916 -0.579151 C -0.420009 -1.410617 -1.967464 H -0.035332 -1.093538 -2.932035 C -1.789845 -1.405314 -1.698776 H -2.484918 -1.102822 -2.476436 C -2.256283 -1.675316 -0.408279 C 3.582168 -0.014120 -0.375398 O 4.475053 -0.986704 -0.715371 H 3.956965 -1.754120 -1.015793 C 4.017125 1.185633 0.186139 H 5.082676 1.329001 0.337477 C 3.095410 2.166552 0.566192 H 3.459307 3.082789 1.025184 C 1.720836 1.980199 0.380403 C 0.704201 2.984438 0.898238 H 0.330454 2.649525 1.877544 C -0.498561 3.307370 -0.019415 H -0.156556 3.590776 -1.019653 H -0.997722 4.194620 0.403119 C -1.639064 2.296867 -0.221501 C -2.134373 1.476871 0.969153 H -1.960587 2.055760 1.886839 H -1.481959 0.598325 1.056519 C -3.620236 1.053595 0.928844 H -4.220267 1.968972 0.840590 H -3.863016 0.631962 1.915057 C -4.121469 0.079266 -0.160459 H -3.841716 0.468893 -1.142327 H -5.218995 0.103838 -0.115735 C -3.704466 -1.409970 -0.049830 H -3.911482 -1.777167 0.964258 H -4.356737 -1.983544 -0.722633 O -2.171116 2.219118 -1.315811 H 1.222738 3.930168 1.096937 C 1.299650 0.790397 -0.222743 H 0.249892 0.623281 -0.414198 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23998119 Predicted Change= -1.005377D-08 Zero-point correction (ZPE)= -1075.8559 0.38406 Internal Energy (U)= -1075.8345 0.40538 Enthalpy (H)= -1075.8336 0.40633 Gibbs Free Energy (G)= -1075.9061 0.33384 ------------------------------------------------------------------------------ Frequencies -- 13.0123 38.1410 53.8785

5.2.8 Intc Supporting Information: 010-GS-C11-12in-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24720199 Predicted Change= -5.661915D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00491 || 0.00180 [ NO ] 0.00491 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.638799 -1.877548 0.532223 H -2.177454 -1.944582 1.471273 C -0.252028 -2.036730 0.516236 O 0.521881 -2.285022 1.603825 C -0.100892 -2.301417 2.881607 H -0.836045 -3.112895 2.959973

H -0.589027 -1.343116 3.098731 H 0.702918 -2.472548 3.599292 C 0.434198 -1.843866 -0.699837 O 1.818366 -1.721986 -0.684355 C 2.274078 -0.445372 -0.351290 C -0.266947 -1.628902 -1.876072 H 0.293574 -1.493512 -2.796337 C -1.659645 -1.495613 -1.849825 H -2.197661 -1.282213 -2.769820 C -2.346545 -1.543740 -0.634625 C 3.661549 -0.261009 -0.451442 O 4.477805 -1.287874 -0.829153 H 3.911961 -2.067846 -0.963061 C 4.190143 0.997007 -0.170262 H 5.263231 1.137340 -0.258225 C 3.350643 2.053762 0.199737 H 3.786321 3.029516 0.401053 C 1.968967 1.872372 0.313040 C 1.031245 2.996995 0.717630 H 0.692491 2.859061 1.753055 C -0.226400 3.126085 -0.169153 H 0.014995 2.942685 -1.222999 H -0.599920 4.161585 -0.123790 C -1.427827 2.266438 0.247221 C -2.396344 1.901200 -0.872091 H -1.905553 1.109927 -1.455855 H -2.454566 2.760901 -1.555193 C -3.822196 1.490824 -0.458188 H -4.438235 1.491763 -1.368714 H -4.227770 2.286930 0.179817 C -4.047816 0.154082 0.278675 H -5.099216 0.149764 0.596388 H -3.448418 0.142082 1.194079 C -3.806426 -1.153943 -0.521994 H -4.357228 -1.959021 -0.016663 H -4.247245 -1.062846 -1.523392 O -1.601178 1.927668 1.405338 H 1.583141 3.943159 0.691937 C 1.449046 0.601580 0.036580 H 0.386682 0.428346 0.134174 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24720199 Predicted Change= -5.661915D-08 Zero-point correction (ZPE)= -1075.8631 0.38408 Internal Energy (U)= -1075.8417 0.40541 Enthalpy (H)= -1075.8408 0.40635 Gibbs Free Energy (G)= -1075.9131 0.33400 ------------------------------------------------------------------------------ Frequencies -- 17.5891 32.2847 50.5014

5.2.9 Intd Supporting Information: 010-GS-Ph-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.25050431 Predicted Change= -1.275605D-08 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00049 || 0.00180 [ YES ] 0.00049 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.586391 1.989660 -0.470989 H 1.919635 2.277293 -1.463090 C 0.231719 2.055756 -0.141814 O -0.764493 2.478597 -0.969288 C -0.425053 2.853157 -2.296313 H 0.025179 2.016260 -2.845653 H 0.264039 3.707505 -2.308495 H -1.364238 3.136610 -2.773695 C -0.184382 1.611937 1.131063 O -1.545129 1.484545 1.390480


S36

S36

C -2.109214 0.360906 0.768805 C 0.749258 1.234058 2.080906 H 0.399030 0.921669 3.059865 C 2.105716 1.179686 1.742959 H 2.825824 0.828864 2.476617 C 2.528276 1.496370 0.450929 C -3.321855 0.572847 0.098267 O -3.887591 1.809634 0.062338 H -3.232524 2.419343 0.448930 C -3.926213 -0.508469 -0.542885 H -4.867016 -0.347412 -1.060365 C -3.299686 -1.757640 -0.552235 H -3.771792 -2.579643 -1.085490 C -2.075398 -1.967525 0.094073 C -1.338314 -3.289767 0.002431 H -1.041663 -3.644998 0.996284 C -0.060969 -3.211240 -0.869308 H -0.261108 -2.663611 -1.797319 H 0.239786 -4.228892 -1.162023 C 1.155896 -2.620781 -0.146724 C 2.021178 -1.645887 -0.934575 H 1.419658 -0.726447 -1.007871 H 2.117406 -2.005050 -1.969462 C 3.397119 -1.342781 -0.322911 H 4.051068 -2.205803 -0.497508 H 3.285544 -1.270161 0.763770 C 4.061384 -0.062450 -0.890021 H 3.639972 0.163678 -1.879116 H 5.130616 -0.242626 -1.057472 C 3.945066 1.197969 0.010642 H 4.570107 1.051355 0.899941 H 4.370050 2.052307 -0.533320 O 1.399595 -2.916257 1.010254 H -2.007213 -4.046095 -0.423067 C -1.502043 -0.887475 0.780624 H -0.564697 -1.016278 1.310726 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.25050431 Predicted Change= -1.275605D-08 Zero-point correction (ZPE)= -1075.8664 0.38402 Internal Energy (U)= -1075.8451 0.40533 Enthalpy (H)= -1075.8442 0.40627 Gibbs Free Energy (G)= -1075.9161 0.33440 ------------------------------------------------------------------------------ Frequencies -- 27.6407 41.8355 57.9036

5.2.10 TSa→ab Supporting Information: 015-TS2-C7-8-COin-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24016172 Predicted Change= -5.470557D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00107 || 0.00180 [ YES ] 0.00107 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.178273 -2.166283 0.647231 H -1.474092 -2.304748 1.681841 C 0.175327 -2.088022 0.310951 O 1.214806 -2.200594 1.183439 C 0.923956 -2.394858 2.560236 H 0.372053 -3.329024 2.725458 H 0.348076 -1.555503 2.970580 H 1.891244 -2.449674 3.061806 C 0.528073 -1.797408 -1.020861 O 1.844706 -1.448484 -1.311077 C 2.168196 -0.176711 -0.814890 C -0.442620 -1.753743 -2.010657 H -0.132764 -1.566344 -3.034448 C -1.792603 -1.858229 -1.666220 H -2.550871 -1.759896 -2.438591 C -2.172509 -1.980423 -0.325332

C 3.380250 -0.073897 -0.120390 O 4.180826 -1.160448 0.043950 H 3.670433 -1.926494 -0.276951 C 3.740574 1.164723 0.413033 H 4.682814 1.247464 0.946011 C 2.877240 2.255513 0.296624 H 3.163551 3.203959 0.745440 C 1.649426 2.151754 -0.372574 C 0.678072 3.314432 -0.412739 H 1.243309 4.245696 -0.296640 C -0.418019 3.296116 0.706930 H -0.675057 4.333668 0.944483 H -0.004777 2.830444 1.608391 C -1.746005 2.640740 0.309713 C -1.974084 1.155653 0.602079 H -1.337773 0.840133 1.434768 H -1.574759 0.627812 -0.273662 C -3.461111 0.776497 0.828964 H -4.053519 1.688098 0.695716 H -3.597049 0.464168 1.873160 C -4.077438 -0.291421 -0.098462 H -3.916772 0.008130 -1.142710 H -5.164591 -0.272901 0.057507 C -3.614663 -1.761763 0.078654 H -3.764096 -2.067448 1.122414 H -4.274040 -2.395496 -0.529545 O -2.595985 3.304790 -0.258357 H 0.182391 3.379520 -1.389211 C 1.325348 0.919778 -0.953607 H 0.396636 0.801634 -1.501560 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24016172 Predicted Change= -5.470557D-10 Zero-point correction (ZPE)= -1075.8564 0.38372 Internal Energy (U)= -1075.8357 0.40440 Enthalpy (H)= -1075.8348 0.40535 Gibbs Free Energy (G)= -1075.9064 0.33367 ------------------------------------------------------------------------------ Frequencies -- -64.3319 12.8045 29.0566

5.2.11 TSa→ac Supporting Information: 015-TS2-C7-8-11-12in-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23137836 Predicted Change= -6.232631D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00107 || 0.00180 [ YES ] 0.00107 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.651683 -1.533558 0.569638 H -2.127301 -1.225823 1.492185 C -0.283793 -1.818365 0.572435 O 0.524639 -1.763949 1.660643 C -0.005454 -1.223844 2.870641 H -0.796918 -1.866409 3.278099 H -0.387131 -0.209671 2.712194 H 0.831958 -1.199967 3.569750 C 0.354148 -2.084384 -0.654936 O 1.744921 -1.994036 -0.720305 C 2.167130 -0.664057 -0.600370 C -0.387816 -2.218638 -1.818639 H 0.134274 -2.430694 -2.747064 C -1.757164 -1.937969 -1.805715 H -2.316771 -1.961179 -2.737481 C -2.382566 -1.512576 -0.628155 C 3.378630 -0.450030 0.068680 O 4.102466 -1.498333 0.548872 H 3.550087 -2.292715 0.434688 C 3.824161 0.862136 0.243785


S37

S37

H 4.765071 1.023015 0.761046 C 3.050117 1.938485 -0.197563 H 3.402910 2.951698 -0.019206 C 1.827960 1.728435 -0.848096 C 0.904181 2.856692 -1.260126 H 1.487297 3.724853 -1.591221 C -0.041090 3.354635 -0.128707 H -0.649227 4.177829 -0.531186 H 0.560840 3.747631 0.696191 C -0.986585 2.322858 0.488388 C -2.148301 1.761237 -0.346910 H -1.757357 0.852399 -0.818757 H -2.381720 2.448692 -1.168561 C -3.400767 1.453188 0.518710 H -4.122157 2.259619 0.345225 H -3.085547 1.552607 1.560662 C -4.167502 0.089878 0.395180 H -5.230314 0.314323 0.244558 H -4.126385 -0.413791 1.368818 C -3.791276 -0.942433 -0.687312 H -4.526384 -1.758421 -0.619066 H -3.936591 -0.503504 -1.683307 O -0.823359 1.968574 1.644049 H 0.303705 2.542317 -2.123105 C 1.419316 0.409860 -1.067877 H 0.488439 0.219854 -1.588857 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23137836 Predicted Change= -6.232631D-09 Zero-point correction (ZPE)= -1075.8469 0.38438 Internal Energy (U)= -1075.8265 0.40485 Enthalpy (H)= -1075.8255 0.40580 Gibbs Free Energy (G)= -1075.8951 0.33624 ------------------------------------------------------------------------------ Frequencies -- -120.1245 25.1713 56.0727

5.2.12 TSa→ad Supporting Information: 015-TS-C7-8-Ph-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.14893094 Predicted Change= -9.501132D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00135 || 0.00180 [ YES ] 0.00135 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.320852 2.720584 -0.084331 H -1.815767 3.673161 -0.243896 C -2.096767 1.626900 0.391050 O -3.443637 1.678743 0.625537 C -4.121312 2.904013 0.403792 H -4.046169 3.224493 -0.644069 H -3.735401 3.701581 1.052381 H -5.167961 2.714608 0.649589 C -1.481316 0.374463 0.637423 O -2.166962 -0.788651 1.071581 C -1.541216 -1.938493 0.527055 C -0.138189 0.293371 0.377034 H 0.412824 -0.601133 0.532960 C 0.571194 1.327338 -0.146763 H 1.581179 1.131368 -0.377427 C 0.054590 2.574020 -0.376527 C -2.101427 -2.426186 -0.656565 O -3.331949 -2.019329 -1.063925 H -3.632696 -1.355457 -0.414666 C -1.329998 -3.268034 -1.466831 H -1.760030 -3.646001 -2.389123 C 0.018246 -3.456944 -1.170323 H 0.642465 -3.971792 -1.897835 C 0.605580 -2.959095 0.007821

C 2.142167 -2.923436 0.092985 H 2.513901 -3.882577 0.483019 C 2.912004 -1.856104 0.946633 H 3.964780 -2.176557 0.892802 H 2.628409 -1.966673 1.997886 C 2.996311 -0.296838 0.785857 C 3.463524 0.434090 -0.509776 H 2.936924 0.027827 -1.383635 H 4.509874 0.120651 -0.646872 C 3.413693 2.020859 -0.451283 H 4.426836 2.364573 -0.686092 H 3.237305 2.296083 0.593513 C 2.435693 2.840014 -1.402188 H 2.148583 2.208860 -2.254217 H 3.036735 3.651185 -1.829789 C 1.128746 3.545654 -0.860286 H 1.407406 4.226201 -0.041863 H 0.756935 4.190526 -1.668279 O 2.842017 0.347188 1.805939 H 2.505958 -2.879040 -0.941180 C -0.256282 -2.342732 0.927815 H 0.125816 -1.956167 1.868184 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.14893094 Predicted Change= -9.501132D-09 Zero-point correction (ZPE)= -1075.7649 0.38397 Internal Energy (U)= -1075.7445 0.40439 Enthalpy (H)= -1075.7435 0.40533 Gibbs Free Energy (G)= -1075.8125 0.33635 ------------------------------------------------------------------------------ Frequencies -- -154.9045 41.1204 47.0713

5.2.13 TSb→ba Supporting Information: 015-TS-COout-C7-8-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.22829521 Predicted Change= -8.680655D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00070 || 0.00180 [ YES ] 0.00070 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -2.077690 -1.805866 0.330208 H -2.834504 -1.850642 1.106519 C -0.752581 -2.153463 0.627359 O -0.308943 -2.570719 1.847206 C -1.265089 -2.762778 2.876583 H -2.024607 -3.501784 2.589449 H -1.764048 -1.822792 3.149408 H -0.705115 -3.134627 3.736496 C 0.224826 -1.975474 -0.365896 O 1.575512 -2.041950 -0.021071 C 2.156280 -0.767059 0.036154 C -0.141163 -1.608975 -1.654460 H 0.637414 -1.497975 -2.403274 C -1.462706 -1.282106 -1.942261 H -1.722099 -0.920266 -2.933469 C -2.427019 -1.298672 -0.929734 C 3.367632 -0.611047 -0.651152 O 3.941988 -1.668186 -1.293383 H 3.349553 -2.428745 -1.152197 C 3.961087 0.650074 -0.683203 H 4.895146 0.774295 -1.222368 C 3.338501 1.730573 -0.054133 H 3.809155 2.709663 -0.102980 C 2.131034 1.580217 0.638550 C 1.520097 2.738771 1.406651 H 1.478312 2.446327 2.464015 C 0.099719 3.301579 1.053547 H 0.210337 4.338687 0.698417


S38

S38

H -0.482675 3.391798 1.976887 C -0.795501 2.663774 -0.014395 C -2.309768 2.870923 0.169264 H -2.670155 3.461833 -0.683502 H -2.501675 3.462936 1.070347 C -3.089597 1.530781 0.239746 H -3.991797 1.679936 0.847016 H -2.478480 0.797070 0.778361 C -3.490517 0.963152 -1.135945 H -2.695877 1.184435 -1.855517 H -4.394439 1.479189 -1.488289 C -3.736802 -0.570315 -1.143609 H -4.466729 -0.841101 -0.369454 H -4.178672 -0.848777 -2.108840 O -0.358706 2.084384 -0.989763 H 2.226398 3.574763 1.368917 C 1.561900 0.302537 0.691455 H 0.629895 0.137793 1.221765 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.22829521 Predicted Change= -8.680655D-10 Zero-point correction (ZPE)= -1075.8446 0.38360 Internal Energy (U)= -1075.8239 0.40434 Enthalpy (H)= -1075.8230 0.40528 Gibbs Free Energy (G)= -1075.8940 0.33422 ------------------------------------------------------------------------------ Frequencies -- -172.4467 27.3605 35.1544

5.2.14 TSb→bc Supporting Information: 015-TS-COout-C11-12out-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.21958629 Predicted Change= -2.168536D-09 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00212 || 0.00180 [ NO ] 0.00212 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -0.766454 -2.714788 0.362182 H -1.355886 -2.997261 1.228592 C 0.595722 -2.428051 0.514279 O 1.292241 -2.532757 1.678917 C 0.624553 -3.061667 2.813967 H 0.233885 -4.068408 2.617629 H -0.199664 -2.412450 3.138934 H 1.375984 -3.110715 3.603767 C 1.275791 -1.847118 -0.571939 O 2.457096 -1.141157 -0.342572 C 2.232106 0.222306 -0.104241 C 0.686649 -1.814653 -1.828894 H 1.254661 -1.402516 -2.657962 C -0.658351 -2.152883 -1.981538 H -1.141939 -1.999576 -2.942528 C -1.423942 -2.464708 -0.852154 C 3.227929 1.083356 -0.584767 O 4.325733 0.589763 -1.223311 H 4.217194 -0.377591 -1.256358 C 3.073994 2.459532 -0.406678 H 3.847802 3.119880 -0.785887 C 1.945700 2.964473 0.240495 H 1.851687 4.039806 0.374003 C 0.946012 2.112734 0.730347 C -0.248822 2.653464 1.500409 H -0.656048 1.860230 2.138983 C -1.401734 3.295956 0.673980 H -0.991343 3.981159 -0.073856 H -2.008583 3.891558 1.373024 C -2.368160 2.364061 -0.063876 C -3.239473 1.418968 0.773006 H -3.993387 2.044654 1.276437

H -2.631119 0.992786 1.582190 C -3.911728 0.286850 -0.029550 H -4.672206 0.708138 -0.695637 H -4.439313 -0.363798 0.680045 C -2.859700 -0.509349 -0.832547 H -1.879402 -0.225448 -0.438844 H -2.845959 -0.161110 -1.868815 C -2.890615 -2.073813 -0.823743 H -3.373608 -2.452529 0.085683 H -3.454687 -2.461855 -1.680167 O -2.489869 2.427024 -1.273692 H 0.108803 3.430580 2.187593 C 1.112606 0.733555 0.549948 H 0.359015 0.052131 0.926318 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.21958629 Predicted Change= -2.168536D-09 Zero-point correction (ZPE)= -1075.8363 0.38326 Internal Energy (U)= -1075.8156 0.40392 Enthalpy (H)= -1075.8147 0.40487 Gibbs Free Energy (G)= -1075.8855 0.33400 ------------------------------------------------------------------------------ Frequencies -- -86.1434 17.0217 43.0912

5.2.15 TSb→bd Supporting Information: 015-TS-COout-Ph-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.15611208 Predicted Change= -4.685577D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00003 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00195 || 0.00180 [ NO ] 0.00195 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -2.458808 1.933336 0.064302 H -3.297395 2.592839 -0.134971 C -2.723034 0.558581 0.313353 O -3.974013 0.005448 0.334088 C -5.089310 0.850111 0.109723 H -5.055386 1.310963 -0.886783 H -5.156745 1.641176 0.868657 H -5.968956 0.207287 0.179846 C -1.652222 -0.345549 0.521645 O -1.838872 -1.733163 0.730813 C -0.641419 -2.441924 0.480416 C -0.382814 0.183845 0.483160 H 0.491012 -0.421467 0.532663 C -0.155659 1.512286 0.295829 H 0.852621 1.825908 0.265726 C -1.139123 2.431847 0.044058 C -0.534384 -3.087201 -0.755461 O -1.628316 -3.292923 -1.534488 H -2.381024 -2.878900 -1.072709 C 0.738643 -3.451125 -1.216966 H 0.818260 -3.955523 -2.174846 C 1.877027 -3.019200 -0.536032 H 2.849283 -3.169264 -0.999500 C 1.783695 -2.345286 0.693178 C 2.933807 -1.533220 1.290333 H 2.589076 -1.074452 2.224695 C 3.610772 -0.421360 0.386724 H 4.052881 -0.929022 -0.477021 H 4.440539 -0.027903 0.989387 C 2.866905 0.795769 -0.251868 C 2.822372 2.142773 0.510057 H 3.870591 2.378239 0.754883 H 2.359140 1.967337 1.491132 C 2.259775 3.448181 -0.186736 H 3.013451 3.711370 -0.939129 H 2.336561 4.225341 0.586520


S39

S39

C 0.891961 3.669091 -0.960172 H 0.827551 2.923208 -1.758390 H 1.059067 4.634288 -1.456668 C -0.536584 3.792765 -0.293737 H -0.476799 4.426754 0.604295 H -1.171552 4.339537 -1.002696 O 2.435635 0.700176 -1.384779 H 3.770615 -2.187905 1.570555 C 0.502358 -2.220115 1.253463 H 0.377986 -1.697736 2.197661 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.15611208 Predicted Change= -4.685577D-08 Zero-point correction (ZPE)= -1075.7719 0.38415 Internal Energy (U)= -1075.7515 0.40456 Enthalpy (H)= -1075.7506 0.40550 Gibbs Free Energy (G)= -1075.8194 0.33664 ------------------------------------------------------------------------------ Frequencies -- -150.1957 46.4318 47.4996

5.2.16 TSc→ca Supporting Information: 015-TS-C11-12out-7-8-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23232467 Predicted Change= -1.212575D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00021 || 0.00180 [ YES ] 0.00021 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.376178 -1.868797 0.653724 H -1.651566 -1.903394 1.702162 C -0.035217 -1.937721 0.291250 O 1.003013 -2.087077 1.156297 C 0.772777 -1.805172 2.534713 H 0.136733 -2.569766 2.999021 H 0.316839 -0.816099 2.656274 H 1.756749 -1.821898 3.005848 C 0.312319 -1.770459 -1.064871 O 1.648634 -1.545194 -1.391772 C 2.110328 -0.340673 -0.836753 C -0.672552 -1.708535 -2.038401 H -0.373756 -1.609187 -3.077798 C -2.021788 -1.667770 -1.661149 H -2.788355 -1.551385 -2.423099 C -2.375568 -1.661700 -0.309720 C 3.296470 -0.408292 -0.093912 O 3.963710 -1.584517 0.045854 H 3.376353 -2.274514 -0.313289 C 3.758933 0.750247 0.529688 H 4.671814 0.698193 1.115090 C 3.020778 1.932066 0.444762 H 3.381429 2.815728 0.965786 C 1.827426 2.003641 -0.285443 C 1.085815 3.320197 -0.415654 H 1.580092 4.045086 0.238492 C -0.463339 3.398187 -0.145064 H -0.949859 3.821583 -1.027927 H -0.623235 4.122279 0.664586 C -1.246882 2.155756 0.313805 C -2.418115 1.711362 -0.568133 H -2.052372 0.864104 -1.162755 H -2.643092 2.507440 -1.286909 C -3.736000 1.330157 0.149134 H -4.519466 1.305555 -0.621727 H -4.006847 2.156524 0.820206 C -3.818977 0.023475 0.961985 H -4.777419 0.047483 1.498477 H -3.034299 0.023928 1.724759 C -3.769617 -1.306956 0.163598

H -4.152573 -2.102977 0.817183 H -4.456475 -1.252731 -0.691196 O -0.967649 1.587376 1.354821 H 1.239531 3.699068 -1.434847 C 1.399641 0.847303 -0.949161 H 0.486598 0.852400 -1.536324 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23232467 Predicted Change= -1.212575D-10 Zero-point correction (ZPE)= -1075.8484 0.38388 Internal Energy (U)= -1075.8277 0.40454 Enthalpy (H)= -1075.8268 0.40549 Gibbs Free Energy (G)= -1075.8971 0.33513 ------------------------------------------------------------------------------ Frequencies -- -172.8175 27.2732 48.1888

5.2.17 TSc→cb Supporting Information: 015-TS2-C11-12in-Coin-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23944556 Predicted Change= -1.195171D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00043 || 0.00180 [ YES ] 0.00043 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.682763 -2.230279 0.263576 H -2.308303 -2.543375 1.093074 C -0.295884 -2.397905 0.336351 O 0.374622 -2.944124 1.385709 C -0.380898 -3.429252 2.485411 H -1.073239 -4.223841 2.178517 H -0.947380 -2.624591 2.972661 H 0.347598 -3.834987 3.189161 C 0.496292 -1.892454 -0.712573 O 1.873819 -1.783978 -0.534732 C 2.269466 -0.496311 -0.163038 C -0.096805 -1.367256 -1.851456 H 0.544222 -1.001138 -2.648074 C -1.484072 -1.222328 -1.919871 H -1.935389 -0.758760 -2.792685 C -2.280676 -1.582870 -0.830390 C 3.559232 -0.113944 -0.554807 O 4.374513 -0.980458 -1.220655 H 3.870840 -1.804026 -1.345958 C 3.989079 1.181434 -0.263094 H 4.987904 1.475917 -0.570333 C 3.137784 2.080493 0.384278 H 3.488632 3.091083 0.580145 C 1.848040 1.702391 0.781267 C 0.888562 2.684276 1.430267 H 0.259629 2.164486 2.163784 C 0.000991 3.495792 0.444311 H 0.545868 3.630525 -0.500392 H -0.148848 4.509289 0.833983 C -1.417134 3.038364 0.045207 C -1.895845 1.606419 0.268629 H -1.783865 1.363512 1.336345 H -1.202606 0.938456 -0.254896 C -3.348570 1.386274 -0.185643 H -3.412392 1.540906 -1.270248 H -3.954021 2.188187 0.251093 C -3.990737 0.032376 0.191977 H -5.078913 0.174648 0.228331 H -3.690970 -0.247061 1.212204 C -3.732721 -1.167882 -0.757682 H -4.350080 -2.008417 -0.412917 H -4.090923 -0.908017 -1.761660 O -2.144818 3.862185 -0.481349 H 1.473786 3.411035 2.005875


S40

S40

C 1.444874 0.389156 0.521325 H 0.464071 0.058204 0.835942 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23944556 Predicted Change= -1.195171D-09 Zero-point correction (ZPE)= -1075.8557 0.38369 Internal Energy (U)= -1075.8351 0.40429 Enthalpy (H)= -1075.8342 0.40523 Gibbs Free Energy (G)= -1075.9043 0.33510 ------------------------------------------------------------------------------ Frequencies -- -45.4853 29.1875 36.8753

5.2.18 TSc→cd Supporting Information: 015-TS-C11-12in-Ph-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.17045872 Predicted Change= -1.171612D-08 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00172 || 0.00180 [ YES ] 0.00172 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.808778 2.999626 -0.085090 H 1.082441 4.039047 -0.234914 C -0.546775 2.690196 0.196969 O -1.542134 3.618988 0.320017 C -1.203969 4.990029 0.199280 H -0.808351 5.223905 -0.798428 H -0.469360 5.293097 0.957163 H -2.133273 5.540996 0.355992 C -0.950446 1.339672 0.349009 O -2.274838 0.976633 0.673432 C -2.504886 -0.405221 0.500881 C 0.026970 0.381674 0.204638 H -0.190753 -0.661220 0.238288 C 1.343955 0.709137 0.052628 H 2.046628 -0.079746 0.129922 C 1.792768 1.989211 -0.148208 C -3.296133 -0.776574 -0.590334 O -4.024590 0.146105 -1.273559 H -3.830942 1.010370 -0.865403 C -3.274971 -2.113210 -1.012198 H -3.904353 -2.404697 -1.847393 C -2.347270 -2.999185 -0.463607 H -2.234620 -3.983842 -0.912724 C -1.518743 -2.627424 0.610679 C -0.217269 -3.375598 0.911722 H 0.196184 -3.067767 1.878286 C 0.887682 -3.145961 -0.196549 H 0.428179 -2.773628 -1.118746 H 1.319481 -4.122369 -0.463984 C 2.121352 -2.270145 0.156509 C 2.862354 -1.612075 -1.037667 H 2.109481 -1.167974 -1.698539 H 3.278477 -2.452786 -1.617766 C 4.063404 -0.625473 -0.803622 H 4.443207 -0.415354 -1.812982 H 4.848074 -1.211970 -0.309900 C 4.061089 0.743077 -0.010853 H 5.121960 1.025882 -0.017960 H 3.820942 0.541248 1.039056 C 3.286189 2.039953 -0.452245 H 3.766114 2.888048 0.054786 H 3.442137 2.212966 -1.528133 O 2.511176 -2.157326 1.302898 H -0.405288 -4.453270 0.977717 C -1.749776 -1.367113 1.182500 H -1.149095 -1.043716 2.026711 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis

Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.17045872 Predicted Change= -1.171612D-08 Zero-point correction (ZPE)= -1075.7860 0.38442 Internal Energy (U)= -1075.7657 0.40473 Enthalpy (H)= -1075.7647 0.40567 Gibbs Free Energy (G)= -1075.8335 0.33694 ------------------------------------------------------------------------------ Frequencies -- -132.0197 46.9147 51.0013

5.2.19 TSd→da Supporting Information: 015-TS-Ph-C7-8in-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23259847 Predicted Change= -3.385843D-11 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00005 || 0.00180 [ YES ] 0.00005 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.145013 -2.324925 -0.365568 H -1.304420 -2.823572 -1.316395 C 0.147510 -2.155670 0.127852 O 1.287943 -2.600849 -0.473256 C 1.191797 -3.199527 -1.757727 H 0.732857 -2.515195 -2.482298 H 0.615935 -4.133233 -1.722780 H 2.217991 -3.413736 -2.059776 C 0.337111 -1.412555 1.311462 O 1.627505 -0.997651 1.645411 C 2.035605 0.055776 0.807642 C -0.753393 -1.005248 2.061423 H -0.580624 -0.460996 2.984519 C -2.048677 -1.199864 1.570228 H -2.892781 -0.805109 2.127084 C -2.248746 -1.783909 0.318449 C 3.175428 -0.159372 0.023979 O 3.880195 -1.318240 0.104344 H 3.321992 -1.940219 0.606765 C 3.558483 0.838956 -0.875455 H 4.434148 0.672510 -1.495425 C 2.786460 1.990488 -1.011499 H 3.081460 2.734846 -1.747923 C 1.639587 2.212112 -0.231134 C 0.881674 3.520425 -0.406003 H 1.338712 4.267038 0.257092 C -0.670919 3.626717 -0.168984 H -1.112617 4.072365 -1.070474 H -0.850298 4.324415 0.652970 C -1.532958 2.407751 0.177588 C -1.878667 1.369673 -0.893010 H -1.194064 0.528788 -0.725889 H -1.650752 1.754483 -1.894506 C -3.346382 0.889703 -0.797866 H -3.980572 1.631288 -1.300226 H -3.636575 0.906126 0.257554 C -3.636252 -0.508390 -1.395814 H -2.940639 -0.716117 -2.220423 H -4.639778 -0.507229 -1.840505 C -3.585667 -1.682991 -0.379434 H -4.379972 -1.539662 0.363643 H -3.816216 -2.613987 -0.914307 O -1.987511 2.299520 1.305093 H 1.093360 3.877395 -1.419565 C 1.299555 1.234130 0.709326 H 0.438575 1.357867 1.355411 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23259847 Predicted Change= -3.385843D-11


S41

S41

Zero-point correction (ZPE)= -1075.8485 0.38409 Internal Energy (U)= -1075.8279 0.40468 Enthalpy (H)= -1075.8269 0.40562 Gibbs Free Energy (G)= -1075.8967 0.33588 ------------------------------------------------------------------------------ Frequencies -- -166.7936 33.9627 54.9006

5.2.20 TSd→db Supporting Information: 015-TS-Ph-COin-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23926222 Predicted Change= -1.406746D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00148 || 0.00180 [ YES ] 0.00148 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.976736 -2.232219 0.686200 H 1.287322 -2.360924 1.718140 C -0.373815 -2.067323 0.379208 O -1.395551 -2.068949 1.278558 C -1.081253 -2.207276 2.657164 H -0.431727 -1.393026 3.002935 H -0.597491 -3.170622 2.863394 H -2.035163 -2.159241 3.184364 C -0.741911 -1.811569 -0.958585 O -2.036180 -1.369380 -1.226884 C -2.223900 -0.049635 -0.788335 C 0.203264 -1.874619 -1.968859 H -0.116857 -1.701354 -2.992039 C 1.554522 -2.057032 -1.650536 H 2.298465 -2.043994 -2.442346 C 1.958855 -2.159659 -0.318398 C -3.403576 0.216378 -0.082809 O -4.318315 -0.765201 0.139409 H -3.904622 -1.596862 -0.155933 C -3.610742 1.509230 0.403545 H -4.527968 1.718897 0.945357 C -2.631329 2.490671 0.235170 H -2.800032 3.480538 0.653082 C -1.435596 2.220442 -0.445354 C -0.318605 3.243967 -0.534618 H 0.200899 3.150896 -1.496388 C 0.718981 3.186452 0.638118 H 0.271717 2.633767 1.476201 H 0.929552 4.196739 1.000340 C 2.097910 2.567984 0.366418 C 2.174992 1.164957 -0.243657 H 1.781123 1.248913 -1.265435 H 1.451103 0.527747 0.276959 C 3.593155 0.547534 -0.255312 H 4.288129 1.336451 0.050309 H 3.869961 0.276781 -1.282151 C 3.809378 -0.678702 0.659153 H 3.276680 -0.526268 1.608192 H 4.874509 -0.734728 0.919516 C 3.418092 -2.059052 0.065876 H 4.041871 -2.252093 -0.816184 H 3.672600 -2.832010 0.803719 O 3.100113 3.192860 0.664511 H -0.757590 4.247701 -0.530165 C -1.269314 0.940230 -0.983611 H -0.368074 0.693516 -1.531293 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23926222 Predicted Change= -1.406746D-09 Zero-point correction (ZPE)= -1075.8555 0.38370 Internal Energy (U)= -1075.8349 0.40431 Enthalpy (H)= -1075.8340 0.40526 Gibbs Free Energy (G)= -1075.9046 0.33464

------------------------------------------------------------------------------ Frequencies -- -30.2912 20.5237 41.7701

5.2.21 TSd→dc Supporting Information: 015-TS2-Ph-C11-12-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23730769 Predicted Change= -9.149541D-09 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00331 || 0.00180 [ NO ] 0.00331 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.161269 -2.058563 0.695376 H 1.391759 -2.291704 1.730028 C -0.166987 -2.035266 0.266135 O -1.253027 -2.297559 1.044161 C -1.044161 -2.589419 2.417784 H -0.554901 -1.753862 2.934989 H -0.443315 -3.498731 2.548770 H -2.037071 -2.746112 2.841968 C -0.445087 -1.635386 -1.055660 O -1.757451 -1.329443 -1.405688 C -2.178218 -0.125166 -0.819861 C 0.588845 -1.416166 -1.951439 H 0.341931 -1.125349 -2.967962 C 1.916579 -1.459448 -1.514789 H 2.708488 -1.217741 -2.216264 C 2.211352 -1.708600 -0.172182 C -3.472495 -0.114893 -0.283188 O -4.263577 -1.220701 -0.354836 H -3.702188 -1.935759 -0.705852 C -3.923041 1.047170 0.343333 H -4.925177 1.057155 0.761137 C -3.073501 2.149923 0.475601 H -3.431683 3.030321 1.004285 C -1.772269 2.135127 -0.040743 C -0.802898 3.282226 0.177800 H -0.459330 3.690344 -0.780351 C 0.449899 2.883125 0.992809 H 0.185580 2.211996 1.819143 H 0.884624 3.780243 1.462518 C 1.594724 2.278737 0.172716 C 2.567615 1.366421 0.925443 H 2.010448 0.434331 1.082823 H 2.714284 1.779126 1.932697 C 3.914949 1.135206 0.201877 H 4.696856 1.615154 0.800460 H 3.866319 1.697715 -0.735102 C 4.398424 -0.316172 -0.137531 H 5.426042 -0.424815 0.230409 H 4.478907 -0.407646 -1.226629 C 3.616544 -1.542370 0.383810 H 4.217333 -2.431698 0.142380 H 3.561833 -1.512092 1.479875 O 1.724952 2.528105 -1.012139 H -1.321613 4.091763 0.703193 C -1.351052 0.984820 -0.720589 H -0.359254 0.946305 -1.154709 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23730769 Predicted Change= -9.149541D-09 Zero-point correction (ZPE)= -1075.8534 0.38387 Internal Energy (U)= -1075.8327 0.40452 Enthalpy (H)= -1075.8318 0.40546 Gibbs Free Energy (G)= -1075.9025 0.33472 ------------------------------------------------------------------------------ Frequencies -- -135.8583 21.8654 37.6122


S42

S42

5.2.22 Intab Supporting Information: 020-GS2-C7-8-COin-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24703549 Predicted Change= -8.652208D-09 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00220 || 0.00180 [ NO ] 0.00220 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.372004 -1.969734 0.596801 H -1.747719 -2.105850 1.605965 C 0.003321 -2.019525 0.348914 O 0.966798 -2.234422 1.287030 C 0.563945 -2.429108 2.633837 H -0.081117 -3.311278 2.737529 H 0.039297 -1.549180 3.028879 H 1.484004 -2.584249 3.199569 C 0.466105 -1.761748 -0.955551 O 1.823586 -1.532661 -1.159285 C 2.217820 -0.265056 -0.711098 C -0.430652 -1.603159 -2.000847 H -0.039132 -1.427964 -2.998335 C -1.802029 -1.564835 -1.742564 H -2.494468 -1.372597 -2.557470 C -2.279046 -1.671056 -0.432731 C 3.503423 -0.186199 -0.157444 O 4.293971 -1.292837 -0.079622 H 3.741485 -2.045437 -0.358443 C 3.948201 1.044817 0.323034 H 4.944098 1.105830 0.751275 C 3.105092 2.160239 0.289813 H 3.460971 3.102968 0.699002 C 1.814441 2.080612 -0.244990 C 0.846774 3.248297 -0.203768 H 1.385827 4.151626 0.102745 C -0.335179 3.021828 0.767321 H -0.757836 3.995022 1.065476 H 0.008867 2.547246 1.693966 C -1.526538 2.245233 0.189514 C -2.337029 1.430771 1.190959 H -2.322130 1.966965 2.150581 H -1.757291 0.513737 1.367964 C -3.797589 1.109186 0.820510 H -4.298289 2.057851 0.586080 H -4.286104 0.729383 1.729338 C -4.101561 0.134939 -0.336732 H -3.633189 0.506030 -1.253016 H -5.186826 0.181920 -0.499141 C -3.731673 -1.360832 -0.134051 H -3.986282 -1.673246 0.887586 H -4.368845 -1.953724 -0.803562 O -1.814145 2.307675 -0.993275 H 0.429516 3.445356 -1.198514 C 1.393774 0.850908 -0.769298 H 0.405910 0.764089 -1.206025 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24703549 Predicted Change= -8.652208D-09 Zero-point correction (ZPE)= -1075.8629 0.38412 Internal Energy (U)= -1075.8416 0.40536 Enthalpy (H)= -1075.8407 0.40630 Gibbs Free Energy (G)= -1075.9124 0.33462 ------------------------------------------------------------------------------ Frequencies -- 27.3889 37.5325 55.0720

5.2.23 Intac Supporting Information: 020-GS-C7-8-11-12in-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24479487 Predicted Change= -9.583150D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00151 || 0.00180 [ YES ] 0.00151 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.465109 -1.701186 0.716713 H -1.832940 -1.550802 1.725046 C -0.097840 -1.854505 0.498437 O 0.855758 -1.850841 1.466693 C 0.479395 -1.432309 2.777153 H -0.199525 -2.155612 3.246999 H 0.008718 -0.442939 2.752532 H 1.408092 -1.388876 3.348356 C 0.372979 -1.940522 -0.828528 O 1.740195 -1.789513 -1.065938 C 2.163817 -0.488395 -0.767144 C -0.519110 -2.011690 -1.886798 H -0.125395 -2.091644 -2.895794 C -1.892920 -1.867591 -1.651766 H -2.582289 -1.858021 -2.492002 C -2.367095 -1.635882 -0.358174 C 3.382235 -0.360075 -0.088637 O 4.120903 -1.457997 0.226680 H 3.567093 -2.231790 0.016035 C 3.812248 0.917810 0.275322 H 4.757963 1.016148 0.799467 C 3.010805 2.033112 0.017141 H 3.347143 3.013290 0.347387 C 1.780782 1.904967 -0.640290 C 0.829223 3.068195 -0.834655 H 1.394062 4.005772 -0.903567 C -0.201436 3.241319 0.316517 H -0.776240 4.159901 0.118419 H 0.322682 3.377304 1.267395 C -1.228680 2.125957 0.539231 C -2.122284 1.713813 -0.629823 H -1.661626 0.829784 -1.086766 H -2.092533 2.499065 -1.396245 C -3.601579 1.413333 -0.286151 H -4.144613 1.343176 -1.239433 H -4.013238 2.293001 0.226674 C -3.945435 0.175479 0.570031 H -4.998679 0.278037 0.865346 H -3.360753 0.209214 1.493225 C -3.799966 -1.217423 -0.095168 H -4.283130 -1.949169 0.567892 H -4.366223 -1.237359 -1.035597 O -1.345831 1.616951 1.642656 H 0.298026 2.959963 -1.788869 C 1.394005 0.628631 -1.060451 H 0.461008 0.494524 -1.594981 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24479487 Predicted Change= -9.583150D-09 Zero-point correction (ZPE)= -1075.8602 0.38455 Internal Energy (U)= -1075.8391 0.40563 Enthalpy (H)= -1075.8382 0.40657 Gibbs Free Energy (G)= -1075.9090 0.33574 ------------------------------------------------------------------------------ Frequencies -- 32.0674 48.1483 62.4286

5.2.24 Intad Supporting Information: 020-GS-C7-8-Ph-Galeon.log


S43

S43

------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24276926 Predicted Change= -3.203420D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00399 || 0.00180 [ NO ] 0.00399 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 2.159676 -1.801970 0.232596 H 2.850322 -2.048838 1.032497 C 0.832420 -2.242222 0.297852 O 0.300628 -2.983542 1.307794 C 1.158643 -3.396275 2.360167 H 1.569865 -2.537577 2.907636 H 1.984974 -4.015061 1.986946 H 0.537470 -3.989003 3.033696 C -0.061919 -1.832326 -0.709756 O -1.431283 -2.033887 -0.532553 C -2.093547 -0.870622 -0.132432 C 0.394483 -1.111215 -1.803394 H -0.319450 -0.815995 -2.566384 C 1.723997 -0.692158 -1.865587 H 2.056250 -0.084782 -2.702152 C 2.600861 -0.976137 -0.815377 C -3.398576 -0.698090 -0.610981 O -3.992447 -1.651118 -1.383751 H -3.336044 -2.358477 -1.513558 C -4.076304 0.481320 -0.294073 H -5.085849 0.613872 -0.670864 C -3.450339 1.477820 0.458783 H -3.987763 2.400531 0.664660 C -2.147094 1.306798 0.943363 C -1.400786 2.388277 1.699733 H -2.104113 2.973251 2.305136 C -0.634293 3.391526 0.796197 H -0.189878 4.160245 1.447927 H -1.332532 3.897289 0.122274 C 0.500047 2.854607 -0.083413 C 1.624052 2.041377 0.565336 H 1.261079 1.008394 0.631838 H 1.774245 2.370963 1.602851 C 2.945925 2.071965 -0.222929 H 3.410346 3.055296 -0.077264 H 2.708448 2.012042 -1.289803 C 3.956558 0.965907 0.168835 H 3.790748 0.660378 1.211298 H 4.973387 1.377412 0.135996 C 3.950601 -0.297153 -0.736425 H 4.268329 -0.004149 -1.744833 H 4.709110 -0.995079 -0.358025 O 0.516857 3.105150 -1.275042 H -0.700867 1.925418 2.406788 C -1.498703 0.101547 0.660931 H -0.502339 -0.076807 1.045199 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24276926 Predicted Change= -3.203420D-08 Zero-point correction (ZPE)= -1075.8588 0.38387 Internal Energy (U)= -1075.8374 0.40532 Enthalpy (H)= -1075.8364 0.40627 Gibbs Free Energy (G)= -1075.9093 0.33341 ------------------------------------------------------------------------------ Frequencies -- 25.4510 33.4616 40.6721

5.2.25 Intba Supporting Information: 020-GS-COout-C7-8-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011

============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24848804 Predicted Change= -1.073140D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00207 || 0.00180 [ NO ] 0.00207 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.242459 -2.179709 0.566731 H -1.579809 -2.370025 1.580325 C 0.124529 -2.112980 0.285266 O 1.127234 -2.285170 1.191864 C 0.776246 -2.533483 2.544447 H 0.202426 -3.463755 2.646994 H 0.197268 -1.702604 2.968335 H 1.720168 -2.628272 3.083562 C 0.532160 -1.766727 -1.016639 O 1.862083 -1.422607 -1.237320 C 2.173374 -0.155992 -0.719612 C -0.399040 -1.651479 -2.037357 H -0.048003 -1.411348 -3.036314 C -1.762739 -1.732546 -1.747430 H -2.488879 -1.558000 -2.536841 C -2.195328 -1.915501 -0.430937 C 3.415361 -0.051122 -0.078100 O 4.234447 -1.133610 0.026026 H 3.720416 -1.895061 -0.299713 C 3.786710 1.180370 0.460376 H 4.749841 1.263374 0.954748 C 2.911061 2.267570 0.392651 H 3.210893 3.213699 0.837688 C 1.659270 2.160741 -0.225963 C 0.683036 3.323157 -0.249171 H 1.211401 4.231234 0.062261 C -0.551703 3.143613 0.661963 H -0.923612 4.126017 0.995551 H -0.288156 2.611648 1.586820 C -1.757187 2.450661 0.027178 C -2.936349 2.143565 0.953931 H -3.840156 2.580103 0.509762 H -2.779614 2.627745 1.924670 C -3.135777 0.618483 1.158302 H -3.697006 0.462782 2.089037 H -2.152817 0.158668 1.314849 C -3.863890 -0.084061 -0.002823 H -3.528568 0.350788 -0.950055 H -4.941350 0.116575 0.076265 C -3.633169 -1.619294 -0.061969 H -3.890478 -2.076822 0.902435 H -4.315418 -2.045281 -0.808164 O -1.796723 2.166346 -1.158003 H 0.324264 3.496806 -1.270492 C 1.310522 0.929743 -0.800098 H 0.353096 0.822003 -1.296749 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24848804 Predicted Change= -1.073140D-08 Zero-point correction (ZPE)= -1075.8642 0.38424 Internal Energy (U)= -1075.8430 0.40544 Enthalpy (H)= -1075.8420 0.40639 Gibbs Free Energy (G)= -1075.9136 0.33482 ------------------------------------------------------------------------------ Frequencies -- 27.1292 39.3599 58.8043

5.2.26 Intbc Supporting Information: 020-GS-COout-C11-12out-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman


S44

S44

#N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24276982 Predicted Change= -1.739104D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00190 || 0.00180 [ NO ] 0.00190 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 2.160589 1.801385 0.232022 H 2.851769 2.048139 1.031496 C 0.833570 2.242270 0.297899 O 0.302690 2.984100 1.307948 C 1.160982 3.394843 2.360859 H 1.987625 4.013748 1.988504 H 1.571797 2.535129 2.907033 H 0.540172 3.986930 3.035285 C -0.061468 1.832717 -0.709214 O -1.430646 2.035011 -0.531452 C -2.093280 0.871811 -0.131775 C 0.394091 1.111319 -1.803039 H -0.320318 0.816440 -2.565716 C 1.723363 0.691580 -1.865828 H 2.054908 0.083967 -2.702506 C 2.600857 0.975184 -0.816035 C -3.397791 0.699047 -0.611556 O -3.991036 1.651841 -1.385088 H -3.334775 2.359513 -1.513911 C -4.075672 -0.480446 -0.295160 H -5.084855 -0.613170 -0.672852 C -3.450192 -1.476816 0.458225 H -3.987605 -2.399638 0.663635 C -2.147374 -1.305579 0.943974 C -1.401525 -2.387159 1.700669 H -0.701228 -1.924401 2.407407 C -0.635776 -3.391072 0.797269 H -1.334429 -3.896836 0.123774 H -0.191445 -4.159775 1.449094 C 0.498515 -2.855041 -0.082934 C 1.622694 -2.041369 0.564919 H 1.772906 -2.369844 1.602786 H 1.259819 -1.008282 0.630240 C 2.944448 -2.073091 -0.223447 H 2.706894 -2.013526 -1.290331 H 3.408252 -3.056661 -0.077380 C 3.955915 -0.967587 0.167639 H 4.972465 -1.379738 0.134197 H 3.790938 -0.661914 1.210195 C 3.950249 0.295465 -0.737665 H 4.709351 0.992945 -0.359630 H 4.267325 0.002233 -1.746207 O 0.515146 -3.106671 -1.274339 H -2.105025 -2.971561 2.306424 C -1.498988 -0.100193 0.662246 H -0.503035 0.078453 1.047496 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24276982 Predicted Change= -1.739104D-08 Zero-point correction (ZPE)= -1075.8588 0.38388 Internal Energy (U)= -1075.8374 0.40533 Enthalpy (H)= -1075.8364 0.40627 Gibbs Free Energy (G)= -1075.9093 0.33343 ------------------------------------------------------------------------------ Frequencies -- 25.7372 33.4958 40.6892

5.2.27 Intbd Supporting Information: 020-GS-COout-Ph-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1

------------------------------------------------------------------------------ SCF Energy= -1076.24494717 Predicted Change= -1.695883D-07 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00007 || 0.00045 [ YES ] 0.00001 || 0.00030 [ YES ] Displ 0.00439 || 0.00180 [ NO ] 0.00439 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.554423 -1.797024 0.773216 H 1.931017 -1.621481 1.774638 C 0.182839 -1.932970 0.567893 O -0.765792 -1.906648 1.540028 C -0.382231 -1.464943 2.840471 H 0.069077 -0.468259 2.793885 H 0.311950 -2.171536 3.313903 H -1.305820 -1.429560 3.420877 C -0.296753 -2.019608 -0.755413 O -1.659340 -1.842882 -0.988860 C -2.081542 -0.535477 -0.726776 C 0.584110 -2.129993 -1.818921 H 0.181050 -2.215034 -2.823742 C 1.961276 -2.004535 -1.596053 H 2.643111 -2.004374 -2.442436 C 2.446268 -1.751036 -0.310635 C -3.370520 -0.408102 -0.190993 O -4.131270 -1.510628 0.049317 H -3.555446 -2.281483 -0.105723 C -3.854320 0.867920 0.098427 H -4.854954 0.962889 0.508794 C -3.046861 1.989013 -0.107474 H -3.435410 2.973260 0.144294 C -1.749350 1.865800 -0.619930 C -0.842843 3.069516 -0.785801 H -0.220574 2.952879 -1.683079 C 0.076002 3.367462 0.439947 H -0.532100 3.387550 1.349322 H 0.523439 4.360674 0.296164 C 1.196956 2.354155 0.653291 C 2.463645 2.509505 -0.198360 H 3.195660 3.041420 0.429898 H 2.250163 3.180579 -1.039444 C 3.070690 1.192434 -0.730612 H 3.785785 1.444902 -1.524989 H 2.269781 0.626870 -1.218561 C 3.765483 0.298842 0.317674 H 3.217670 0.371044 1.260363 H 4.781635 0.671778 0.506810 C 3.840739 -1.200069 -0.088731 H 4.438244 -1.316598 -1.001987 H 4.364487 -1.748994 0.705098 O 1.095373 1.476826 1.494800 H -1.453554 3.964751 -0.952276 C -1.288619 0.584519 -0.947247 H -0.293335 0.452905 -1.357916 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24494717 Predicted Change= -1.695883D-07 Zero-point correction (ZPE)= -1075.8607 0.38421 Internal Energy (U)= -1075.8395 0.40541 Enthalpy (H)= -1075.8385 0.40635 Gibbs Free Energy (G)= -1075.9099 0.33496 ------------------------------------------------------------------------------ Frequencies -- 26.0380 50.4363 54.2217

5.2.28 Intca Supporting Information: 020-GS-C11-12in-7-8-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24479495 Predicted Change= -9.900268D-09 ==============================================================================


S45

S45

Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00194 || 0.00180 [ NO ] 0.00194 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.464608 -1.701844 0.716523 H -1.832218 -1.551926 1.725009 C -0.097385 -1.855001 0.497867 O 0.856420 -1.851878 1.465952 C 0.480553 -1.433396 2.776586 H -0.198195 -2.156725 3.246647 H 0.009853 -0.444016 2.752194 H 1.409472 -1.389986 3.347412 C 0.373168 -1.940363 -0.829234 O 1.740326 -1.789133 -1.066878 C 2.163773 -0.488042 -0.767603 C -0.519163 -2.011224 -1.887325 H -0.125681 -2.090730 -2.896456 C -1.892928 -1.867312 -1.651916 H -2.582472 -1.857420 -2.492003 C -2.366839 -1.636133 -0.358130 C 3.381700 -0.359733 -0.088236 O 4.120214 -1.457631 0.227468 H 3.566467 -2.231432 0.016646 C 3.811367 0.918150 0.276190 H 4.756715 1.016491 0.801001 C 3.009970 2.033392 0.017685 H 3.345982 3.013548 0.348333 C 1.780368 1.905235 -0.640547 C 0.828778 3.068416 -0.835093 H 1.393573 4.006005 -0.904327 C -0.201669 3.241779 0.316216 H -0.776651 4.160220 0.118028 H 0.322611 3.378089 1.266976 C -1.228717 2.126341 0.539444 C -2.122534 1.713827 -0.629303 H -1.661704 0.829927 -1.086317 H -2.093286 2.499024 -1.395808 C -3.601640 1.412974 -0.285144 H -4.145017 1.342887 -1.238218 H -4.013252 2.292464 0.227995 C -3.945038 0.174905 0.570929 H -4.998167 0.277284 0.866625 H -3.360031 0.208518 1.493934 C -3.799662 -1.217810 -0.094651 H -4.282626 -1.949785 0.568285 H -4.366132 -1.237490 -1.034968 O -1.345592 1.617595 1.643018 H 0.297437 2.959925 -1.789177 C 1.394009 0.628952 -1.061244 H 0.461359 0.494829 -1.596368 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24479495 Predicted Change= -9.900268D-09 Zero-point correction (ZPE)= -1075.8602 0.38455 Internal Energy (U)= -1075.8391 0.40563 Enthalpy (H)= -1075.8382 0.40657 Gibbs Free Energy (G)= -1075.9090 0.33574 ------------------------------------------------------------------------------ Frequencies -- 32.0496 48.1335 62.3924

5.2.29 Intcb Supporting Information: 020-GS2-C11-12in-Coin-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24276995 Predicted Change= -1.184308D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00180 || 0.00180 [ YES ] 0.00180 || 0.00180 [ YES ]

------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -2.160560 -1.801230 0.231943 H -2.851785 -2.047935 1.031391 C -0.833586 -2.242217 0.297860 O -0.302798 -2.984096 1.307925 C -1.161624 -3.396445 2.359788 H -1.988041 -4.014809 1.986052 H -1.572742 -2.537564 2.907050 H -0.541132 -3.989502 3.033650 C 0.061568 -1.832602 -0.709154 O 1.430722 -2.035016 -0.531259 C 2.093397 -0.871799 -0.131626 C -0.393864 -1.111077 -1.802932 H 0.320620 -0.816179 -2.565534 C -1.723113 -0.691266 -1.865780 H -2.054570 -0.083536 -2.702406 C -2.600695 -0.974916 -0.816086 C 3.397867 -0.699007 -0.611469 O 3.991143 -1.651788 -1.384995 H 3.334884 -2.359454 -1.513861 C 4.075715 0.480535 -0.295129 H 5.084873 0.613286 -0.672879 C 3.450246 1.476896 0.458248 H 3.987646 2.399741 0.663592 C 2.147449 1.305637 0.944075 C 1.401548 2.387173 1.700744 H 0.701242 1.924372 2.407444 C 0.635696 3.391088 0.797385 H 1.334286 3.896964 0.123909 H 0.191333 4.159675 1.449319 C -0.498550 2.854985 -0.082818 C -1.622729 2.041299 0.565010 H -1.772808 2.369527 1.602970 H -1.259974 1.008156 0.630008 C -2.944613 2.073415 -0.223157 H -2.707304 2.014329 -1.290123 H -3.408355 3.056931 -0.076511 C -3.956040 0.967781 0.167597 H -4.972617 1.379863 0.133845 H -3.791344 0.662143 1.210208 C -3.950088 -0.295173 -0.737800 H -4.709235 -0.992734 -0.360022 H -4.266993 -0.001832 -1.746373 O -0.515191 3.106602 -1.274229 H 2.104969 2.971644 2.306517 C 1.499121 0.100211 0.662398 H 0.503168 -0.078429 1.047644 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24276995 Predicted Change= -1.184308D-08 Zero-point correction (ZPE)= -1075.8588 0.38388 Internal Energy (U)= -1075.8374 0.40533 Enthalpy (H)= -1075.8364 0.40627 Gibbs Free Energy (G)= -1075.9093 0.33343 ------------------------------------------------------------------------------ Frequencies -- 25.7474 33.5412 40.6737

5.2.30 Intcd Supporting Information: 020-GS-C11-12in-Ph-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24703547 Predicted Change= -3.643178D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00467 || 0.00180 [ NO ] 0.00467 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------


S46

S46

C 1.371973 -1.969763 0.596642 H 1.747701 -2.105941 1.605788 C -0.003352 -2.019539 0.348799 O -0.966773 -2.234404 1.286983 C -0.563691 -2.430351 2.633533 H -0.039077 -1.550750 3.029358 H 0.081492 -3.312546 2.736242 H -1.483641 -2.586117 3.199272 C -0.466180 -1.761643 -0.955627 O -1.823677 -1.532520 -1.159317 C -2.217857 -0.264910 -0.711049 C 0.430540 -1.603028 -2.000943 H 0.039002 -1.427820 -2.998420 C 1.801927 -1.564683 -1.742704 H 2.494329 -1.372369 -2.557624 C 2.278979 -1.670962 -0.432896 C -3.503464 -0.186054 -0.157402 O -4.294040 -1.292682 -0.079697 H -3.741477 -2.045276 -0.358397 C -3.948187 1.044949 0.323173 H -4.944049 1.105958 0.751492 C -3.105040 2.160353 0.289981 H -3.460856 3.103078 0.699233 C -1.814408 2.080710 -0.244866 C -0.846695 3.248383 -0.203594 H -0.429421 3.445500 -1.198325 C 0.335213 3.021816 0.767503 H -0.008873 2.547175 1.694103 H 0.757909 3.994966 1.065761 C 1.526581 2.245233 0.189690 C 2.337049 1.430704 1.191079 H 1.757314 0.513648 1.367976 H 2.322114 1.966785 2.150766 C 3.797613 1.109156 0.820579 H 4.286165 0.729248 1.729343 H 4.298320 2.057836 0.586221 C 4.101503 0.135037 -0.336787 H 5.186751 0.182016 -0.499278 H 3.633085 0.506253 -1.253004 C 3.731621 -1.360739 -0.134219 H 4.368791 -1.953622 -0.803742 H 3.986217 -1.673215 0.887407 O 1.814229 2.307747 -0.993090 H -1.385754 4.151702 0.102933 C -1.393790 0.851024 -0.769245 H -0.405959 0.764203 -1.206030 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24703547 Predicted Change= -3.643178D-08 Zero-point correction (ZPE)= -1075.8629 0.38412 Internal Energy (U)= -1075.8416 0.40536 Enthalpy (H)= -1075.8407 0.40630 Gibbs Free Energy (G)= -1075.9124 0.33462 ------------------------------------------------------------------------------ Frequencies -- 27.3903 37.5464 55.0698

5.2.31 Intda Supporting Information: 020-GS-Ph-C7-8in-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24276895 Predicted Change= -2.138833D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00295 || 0.00180 [ NO ] 0.00295 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 2.159158 -1.802536 0.232653 H 2.849738 -2.049523 1.032573 C 0.831819 -2.242508 0.297990 O 0.299924 -2.983593 1.308040

C 1.157500 -3.395047 2.361221 H 1.568631 -2.535685 2.907752 H 1.983930 -4.014427 1.989134 H 0.536052 -3.986850 3.035307 C -0.062484 -1.832687 -0.709673 O -1.431877 -2.033957 -0.532469 C -2.093805 -0.870462 -0.132385 C 0.394052 -1.111912 -1.803481 H -0.319815 -0.816773 -2.566554 C 1.723640 -0.693083 -1.865767 H 2.055970 -0.085999 -2.702489 C 2.600467 -0.976969 -0.815486 C -3.398629 -0.697372 -0.611293 O -3.992626 -1.650066 -1.384323 H -3.336634 -2.357895 -1.513616 C -4.075950 0.482310 -0.294443 H -5.085368 0.615319 -0.671444 C -3.449702 1.478525 0.458571 H -3.986750 2.401460 0.664354 C -2.146638 1.306939 0.943436 C -1.400033 2.388155 1.699914 H -2.103189 2.973096 2.305556 C -0.633567 3.391540 0.796505 H -0.189186 4.160163 1.448395 H -1.331797 3.897447 0.122689 C 0.500894 2.855001 -0.083228 C 1.624526 2.040961 0.565073 H 1.261053 1.008130 0.631189 H 1.775005 2.370046 1.602725 C 2.946308 2.071216 -0.223317 H 3.410944 3.054458 -0.077721 H 2.708756 2.011343 -1.290191 C 3.956716 0.964943 0.168367 H 3.791032 0.659535 1.210890 H 4.973649 1.376207 0.135275 C 3.950359 -0.298227 -0.736790 H 4.267939 -0.005345 -1.745281 H 4.708824 -0.996240 -0.358444 O 0.518122 3.106721 -1.274598 H -0.700043 1.925031 2.406741 C -1.498722 0.101396 0.661170 H -0.502544 -0.077454 1.045732 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24276895 Predicted Change= -2.138833D-08 Zero-point correction (ZPE)= -1075.8588 0.38387 Internal Energy (U)= -1075.8374 0.40532 Enthalpy (H)= -1075.8364 0.40627 Gibbs Free Energy (G)= -1075.9093 0.33341 ------------------------------------------------------------------------------ Frequencies -- 25.5205 33.4567 40.6706

5.2.32 Intdb Supporting Information: 020-GS-Ph-COin-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24479493 Predicted Change= -2.215688D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00254 || 0.00180 [ NO ] 0.00254 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.465298 -1.701409 0.716572 H 1.833285 -1.551341 1.724892 C 0.098015 -1.854630 0.498382 O -0.855488 -1.851216 1.466742 C -0.479130 -1.432779 2.777218 H -0.008319 -0.443471 2.752694 H 0.199674 -2.156203 3.247063 H -1.407840 -1.389216 3.348390


S47

S47

C -0.372934 -1.940392 -0.828563 O -1.740199 -1.789486 -1.065799 C -2.163862 -0.488401 -0.767004 C 0.519049 -2.011300 -1.886927 H 0.125253 -2.091075 -2.895911 C 1.892882 -1.867243 -1.651998 H 2.582156 -1.857444 -2.492309 C 2.367190 -1.635859 -0.358396 C -3.382409 -0.360117 -0.088668 O -4.121077 -1.458074 0.226526 H -3.567215 -2.231842 0.015929 C -3.812541 0.917754 0.275151 H -4.758345 1.016086 0.799132 C -3.011100 2.033088 0.017061 H -3.347570 3.013262 0.347218 C -1.780949 1.904982 -0.640102 C -0.829393 3.068229 -0.834361 H -0.298232 2.960141 -1.788611 C 0.201326 3.241288 0.316769 H -0.322700 3.377076 1.267730 H 0.775995 4.159970 0.118711 C 1.228742 2.126051 0.539366 C 2.122219 1.713906 -0.629763 H 2.092366 2.499138 -1.396208 H 1.661517 0.829871 -1.086628 C 3.601556 1.413413 -0.286303 H 4.013292 2.293022 0.226546 H 4.144438 1.343315 -1.239663 C 3.945529 0.175523 0.569767 H 3.360910 0.209199 1.493017 H 4.998799 0.278057 0.864949 C 3.800044 -1.217427 -0.095370 H 4.366370 -1.237471 -1.035758 H 4.283113 -1.949072 0.567852 O 1.346178 1.617247 1.642861 H -1.394235 4.005811 -0.903114 C -1.394044 0.628632 -1.060171 H -0.460952 0.494572 -1.594537 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24479493 Predicted Change= -2.215688D-08 Zero-point correction (ZPE)= -1075.8602 0.38455 Internal Energy (U)= -1075.8391 0.40563 Enthalpy (H)= -1075.8382 0.40657 Gibbs Free Energy (G)= -1075.9090 0.33574 ------------------------------------------------------------------------------ Frequencies -- 32.0665 48.1388 62.4367

5.2.33 Intdc Supporting Information: 020-GS-Ph-C11-12-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24703545 Predicted Change= -9.452867D-09 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00192 || 0.00180 [ NO ] 0.00192 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.372275 -1.969767 0.596930 H 1.748142 -2.105828 1.606046 C -0.003076 -2.019648 0.349218 O -0.966423 -2.234634 1.287438 C -0.563573 -2.427243 2.634538 H -0.038831 -1.546748 3.028179 H 0.081401 -3.309317 2.739628 H -1.483635 -2.581426 3.200528 C -0.466039 -1.762052 -0.955226 O -1.823555 -1.533053 -1.158807 C -2.217830 -0.265379 -0.710912 C 0.430572 -1.603549 -2.000654

H 0.038924 -1.428479 -2.998113 C 1.801980 -1.565107 -1.742537 H 2.494319 -1.372945 -2.557550 C 2.279167 -1.671133 -0.432756 C -3.503587 -0.186408 -0.157600 O -4.294163 -1.293029 -0.079822 H -3.741629 -2.045661 -0.358453 C -3.948471 1.044678 0.322576 H -4.944474 1.105778 0.750560 C -3.105340 2.160097 0.289376 H -3.461324 3.102900 0.698297 C -1.814560 2.080362 -0.245077 C -0.846944 3.248117 -0.203919 H -0.429744 3.445169 -1.198695 C 0.335033 3.021811 0.767155 H -0.008958 2.547230 1.693821 H 0.757579 3.995064 1.065289 C 1.526499 2.245379 0.189371 C 2.336957 1.430815 1.190733 H 1.757253 0.513730 1.367581 H 2.321982 1.966867 2.150434 C 3.797540 1.109300 0.820287 H 4.286091 0.729507 1.729097 H 4.298194 2.057984 0.585850 C 4.101481 0.135082 -0.336987 H 5.186718 0.182183 -0.499556 H 3.632951 0.506111 -1.253218 C 3.731812 -1.360758 -0.134320 H 4.368937 -1.953492 -0.804016 H 3.986660 -1.673231 0.887236 O 1.814201 2.308035 -0.993396 H -1.386088 4.151413 0.102528 C -1.393756 0.850567 -0.769070 H -0.405789 0.763669 -1.205540 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24703545 Predicted Change= -9.452867D-09 Zero-point correction (ZPE)= -1075.8629 0.38412 Internal Energy (U)= -1075.8416 0.40536 Enthalpy (H)= -1075.8407 0.40630 Gibbs Free Energy (G)= -1075.9124 0.33462 ------------------------------------------------------------------------------ Frequencies -- 27.3740 37.4898 55.0632

5.2.34 TSab→abc Supporting Information: 025-TS-C7-8-COin-C11-12out-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.22725935 Predicted Change= -5.896296D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00125 || 0.00180 [ YES ] 0.00125 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -0.522845 -2.406286 0.674982 H -0.921804 -2.482570 1.681454 C 0.815265 -2.058414 0.482049 O 1.723406 -1.840453 1.470880 C 1.296606 -1.973154 2.818284 H 0.935651 -2.988477 3.027286 H 0.507408 -1.250198 3.062999 H 2.176527 -1.767728 3.429869 C 1.259578 -1.794125 -0.829739 O 2.433863 -1.067513 -1.009272 C 2.283967 0.280203 -0.649665 C 0.451053 -2.094410 -1.914956 H 0.834268 -1.911664 -2.914503 C -0.880838 -2.475429 -1.710922 H -1.538264 -2.597328 -2.567771 C -1.403385 -2.517099 -0.415408


S48

S48

C 3.443022 0.914547 -0.178360 O 4.620131 0.233620 -0.090377 H 4.421987 -0.693763 -0.312488 C 3.363238 2.251487 0.208731 H 4.262390 2.738612 0.573619 C 2.141021 2.931524 0.162244 H 2.099397 3.965921 0.495049 C 0.977912 2.301502 -0.290923 C -0.383569 2.977134 -0.296244 H -0.267299 4.049169 -0.105211 C -1.369191 2.359231 0.729317 H -1.452366 2.981400 1.633843 H -0.985954 1.397184 1.094004 C -2.789639 2.115879 0.216360 C -3.696916 1.231983 1.088566 H -4.538918 1.847937 1.430462 H -3.149225 0.905317 1.981105 C -4.227490 -0.001427 0.314367 H -4.978696 0.332066 -0.408336 H -4.742716 -0.660227 1.024525 C -3.079422 -0.746728 -0.410963 H -2.135869 -0.283749 -0.107664 H -3.144609 -0.569270 -1.490014 C -2.882408 -2.275569 -0.176167 H -3.154704 -2.542141 0.852828 H -3.521580 -2.862485 -0.846340 O -3.190711 2.562060 -0.842374 H -0.843311 2.896020 -1.288572 C 1.078497 0.968372 -0.718738 H 0.197440 0.458934 -1.093893 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.22725935 Predicted Change= -5.896296D-09 Zero-point correction (ZPE)= -1075.8436 0.38363 Internal Energy (U)= -1075.8229 0.40428 Enthalpy (H)= -1075.8220 0.40522 Gibbs Free Energy (G)= -1075.8925 0.33470 ------------------------------------------------------------------------------ Frequencies -- -93.1854 29.2201 43.6421

5.2.35 TSab→abd Supporting Information: 025-TS-C7-8-COout-Ph-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.16692316 Predicted Change= -2.838760D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00218 || 0.00180 [ NO ] 0.00218 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.817784 2.446088 0.008446 H 2.445180 3.300201 0.242534 C 2.446966 1.219656 -0.334292 O 3.799829 1.031548 -0.382350 C 4.646487 2.130485 -0.089637 H 4.494065 2.498037 0.933988 H 4.493065 2.957589 -0.795550 H 5.666690 1.755415 -0.190386 C 1.657386 0.080185 -0.621406 O 2.189332 -1.199092 -0.911351 C 1.258183 -2.199529 -0.528100 C 0.296155 0.246779 -0.553604 H -0.368895 -0.568556 -0.694411 C -0.295384 1.424602 -0.209670 H -1.354507 1.403452 -0.135076 C 0.412502 2.563055 0.092334 C 1.427417 -2.735223 0.753043 O 2.594270 -2.566861 1.430051 H 3.166423 -2.014527 0.865305 C 0.340502 -3.369214 1.365523

H 0.469418 -3.778488 2.362605 C -0.919548 -3.306153 0.770764 H -1.783660 -3.638396 1.339585 C -1.108674 -2.764557 -0.510581 C -2.506365 -2.381566 -1.004538 H -2.678319 -2.797837 -2.006658 C -2.873611 -0.854678 -1.125065 H -3.838247 -0.800597 -1.651181 H -2.174718 -0.330756 -1.791967 C -3.033179 -0.017266 0.166163 C -3.681036 1.412760 0.084719 H -4.193803 1.510823 1.048128 H -4.457388 1.365202 -0.690967 C -2.906403 2.768380 -0.173569 H -3.709637 3.507762 -0.281735 H -2.418828 2.736152 -1.153945 C -1.911538 3.297793 0.930872 H -1.810695 2.545697 1.722410 H -2.379156 4.168912 1.404492 C -0.468131 3.740559 0.498301 H -0.541171 4.467514 -0.325100 H -0.021549 4.288278 1.338561 O -2.780700 -0.495973 1.255025 H -3.245841 -2.848506 -0.344971 C 0.044252 -2.362423 -1.207723 H -0.042845 -1.922736 -2.198547 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.16692316 Predicted Change= -2.838760D-08 Zero-point correction (ZPE)= -1075.7826 0.38429 Internal Energy (U)= -1075.7623 0.40460 Enthalpy (H)= -1075.7613 0.40555 Gibbs Free Energy (G)= -1075.8301 0.33680 ------------------------------------------------------------------------------ Frequencies -- -146.6749 38.7761 51.8281

5.2.36 TSac→acb Supporting Information: 025-TS-C7-8-11-12in-COin-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23926221 Predicted Change= -6.022221D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00134 || 0.00180 [ YES ] 0.00134 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -0.976640 -2.232054 0.686248 H -1.287308 -2.360559 1.718186 C 0.373929 -2.067211 0.379330 O 1.395600 -2.068642 1.278754 C 1.081179 -2.206742 2.657355 H 0.597366 -3.170039 2.863690 H 0.431646 -1.392416 3.002940 H 2.035040 -2.158656 3.184640 C 0.742116 -1.811723 -0.958488 O 2.036374 -1.369481 -1.226754 C 2.223922 -0.049677 -0.788295 C -0.202979 -1.874995 -1.968823 H 0.117221 -1.701914 -2.992010 C -1.554263 -2.057366 -1.650567 H -2.298159 -2.044482 -2.442423 C -1.958688 -2.159730 -0.318438 C 3.403492 0.216501 -0.082657 O 4.318279 -0.764988 0.139737 H 3.904693 -1.596692 -0.155635 C 3.610502 1.509420 0.403596 H 4.527646 1.719222 0.945493 C 2.631023 2.490759 0.235000 H 2.799595 3.480697 0.652795 C 1.435400 2.220357 -0.445648


S49

S49

C 0.318335 3.243775 -0.535199 H 0.757270 4.247535 -0.531239 C -0.719091 3.186728 0.637680 H -0.929716 4.197158 0.999472 H -0.271705 2.634469 1.475981 C -2.097992 2.568000 0.366449 C -2.174953 1.164901 -0.243516 H -1.451046 0.527810 0.277251 H -1.780978 1.248752 -1.265256 C -3.593093 0.547417 -0.255274 H -3.869860 0.276767 -1.282151 H -4.288070 1.336297 0.050433 C -3.809379 -0.678911 0.659050 H -4.874546 -0.734991 0.919255 H -3.276844 -0.526538 1.608195 C -3.417962 -2.059205 0.065733 H -3.672485 -2.832220 0.803513 H -4.041662 -2.252230 -0.816386 O -3.100205 3.192691 0.664889 H -0.201286 3.150271 -1.496860 C 1.269264 0.940070 -0.983773 H 0.368066 0.693224 -1.531474 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23926221 Predicted Change= -6.022221D-09 Zero-point correction (ZPE)= -1075.8555 0.38370 Internal Energy (U)= -1075.8349 0.40431 Enthalpy (H)= -1075.8340 0.40526 Gibbs Free Energy (G)= -1075.9046 0.33464 ------------------------------------------------------------------------------ Frequencies -- -30.2153 20.5541 41.7847

5.2.37 TSac→acd Supporting Information: 025-TS-C7-8-11-12in-Ph-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.14964813 Predicted Change= -3.104044D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00082 || 0.00180 [ YES ] 0.00082 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -2.853670 1.252550 -0.076512 H -3.821111 1.689308 -0.302514 C -2.784048 -0.145579 0.166683 O -3.862251 -0.983960 0.168241 C -5.148780 -0.432261 -0.056376 H -5.225048 0.026411 -1.051421 H -5.405596 0.315953 0.705260 H -5.846866 -1.268886 0.008977 C -1.527771 -0.758214 0.400888 O -1.361487 -2.135776 0.666549 C -0.000869 -2.512240 0.522282 C -0.432100 0.070978 0.383072 H 0.555218 -0.313210 0.456617 C -0.529966 1.426357 0.276574 H 0.369820 1.980060 0.405750 C -1.704576 2.072225 -0.017969 C 0.341812 -3.134872 -0.682742 O -0.614554 -3.651736 -1.499353 H -1.473327 -3.457570 -1.080571 C 1.684813 -3.141739 -1.078770 H 1.949406 -3.625496 -2.013846 C 2.620020 -2.388350 -0.368537 H 3.611627 -2.249686 -0.789428 C 2.289323 -1.744824 0.835906 C 3.163959 -0.618915 1.394013 H 3.248017 -0.706049 2.485110 C 2.679850 0.860880 1.120843 H 3.391292 1.523586 1.639513

H 1.717560 1.055833 1.599497 C 2.705937 1.326105 -0.352515 C 1.898312 2.509820 -1.040571 H 1.146894 1.982790 -1.641211 H 2.643716 2.844003 -1.771048 C 1.267862 3.849089 -0.486327 H 1.236193 4.474779 -1.388192 H 2.008807 4.334005 0.163896 C -0.121386 4.088212 0.234385 H -0.204056 5.182761 0.246785 H -0.046661 3.796761 1.289174 C -1.497161 3.555647 -0.303711 H -2.286604 4.167832 0.152812 H -1.567681 3.739470 -1.386410 O 3.445688 0.732670 -1.116827 H 4.174084 -0.715967 0.986114 C 0.995676 -1.967436 1.342557 H 0.681725 -1.470878 2.257229 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.14964813 Predicted Change= -3.104044D-09 Zero-point correction (ZPE)= -1075.7647 0.38485 Internal Energy (U)= -1075.7446 0.40501 Enthalpy (H)= -1075.7436 0.40595 Gibbs Free Energy (G)= -1075.8123 0.33733 ------------------------------------------------------------------------------ Frequencies -- -121.2655 27.6280 59.7233

5.2.38 TSad→adb Supporting Information: 025-TS1-C7-8-Ph-COin-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23944552 Predicted Change= -2.118491D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00095 || 0.00180 [ YES ] 0.00095 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.683096 -2.230138 0.263557 H 2.308656 -2.543252 1.093033 C 0.296228 -2.397936 0.336293 O -0.374233 -2.944371 1.385570 C 0.381332 -3.429606 2.485195 H 0.947710 -2.624967 2.972600 H 1.073776 -4.224051 2.178156 H -0.347124 -3.835561 3.188861 C -0.495988 -1.892459 -0.712588 O -1.873538 -1.784164 -0.534777 C -2.269361 -0.496564 -0.163036 C 0.097067 -1.367079 -1.851408 H -0.543988 -1.000951 -2.647998 C 1.484320 -1.222006 -1.919799 H 1.935598 -0.758305 -2.792562 C 2.280955 -1.582561 -0.830344 C -3.559137 -0.114322 -0.554894 O -4.374252 -0.980878 -1.220887 H -3.870451 -1.804362 -1.346239 C -3.989158 1.180991 -0.263123 H -4.987986 1.475391 -0.570437 C -3.138017 2.080098 0.384385 H -3.488989 3.090642 0.580271 C -1.848261 1.702119 0.781456 C -0.888940 2.684126 1.430505 H -1.474295 3.410781 2.006113 C -0.001540 3.495789 0.444542 H 0.148282 4.509268 0.834259 H -0.546573 3.630594 -0.500065 C 1.416570 3.038514 0.045198 C 1.895568 1.606679 0.268681 H 1.202380 0.938559 -0.254717


S50

S50

H 1.783753 1.363835 1.336428 C 3.348285 1.386748 -0.185708 H 3.953633 2.188816 0.250886 H 3.411977 1.541293 -1.270331 C 3.990714 0.033002 0.192014 H 3.690978 -0.246431 1.212252 H 5.078862 0.175483 0.228383 C 3.732944 -1.167357 -0.757585 H 4.091150 -0.907481 -1.761558 H 4.350410 -2.007780 -0.412739 O 2.143995 3.862412 -0.481598 H -0.259922 2.164452 2.164035 C -1.444928 0.388950 0.521458 H -0.464101 0.058093 0.836111 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23944552 Predicted Change= -2.118491D-09 Zero-point correction (ZPE)= -1075.8557 0.38369 Internal Energy (U)= -1075.8351 0.40428 Enthalpy (H)= -1075.8342 0.40523 Gibbs Free Energy (G)= -1075.9043 0.33510 ------------------------------------------------------------------------------ Frequencies -- -45.4941 29.1975 36.8790

5.2.39 TSad→adc Supporting Information: 025-TS2-C7-8-Ph-C11-12in-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.22710519 Predicted Change= -2.173486D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00108 || 0.00180 [ YES ] 0.00108 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.575049 -2.192359 0.446130 H 2.047839 -2.592721 1.337352 C 0.206294 -2.390190 0.238576 O -0.624239 -3.068819 1.075105 C -0.064195 -3.676106 2.228922 H 0.373443 -2.930498 2.906041 H 0.702068 -4.415818 1.962739 H -0.892713 -4.177421 2.731937 C -0.401187 -1.750747 -0.858988 O -1.787428 -1.604786 -0.876801 C -2.197103 -0.387536 -0.328187 C 0.369657 -1.075516 -1.792089 H -0.130786 -0.583350 -2.620273 C 1.740105 -0.904799 -1.586870 H 2.300506 -0.294563 -2.285787 C 2.337852 -1.389985 -0.421405 C -3.505799 0.014459 -0.633700 O -4.319046 -0.773981 -1.393613 H -3.801886 -1.559143 -1.644839 C -3.958508 1.243653 -0.154227 H -4.971033 1.550315 -0.398194 C -3.118001 2.065479 0.604275 H -3.489122 3.027231 0.950434 C -1.814844 1.665295 0.916393 C -0.842412 2.528046 1.695714 H -1.395429 3.261138 2.294997 C 0.163750 3.325261 0.816801 H 0.748967 3.976501 1.482701 H -0.391984 3.961418 0.121435 C 1.154375 2.524524 -0.033798 C 2.273574 1.726676 0.659952 H 1.874023 0.717634 0.815174 H 2.449206 2.133336 1.663146 C 3.583476 1.694450 -0.176946 H 4.321644 2.307775 0.351464 H 3.366705 2.218854 -1.111009

C 4.277607 0.340266 -0.557663 H 5.328333 0.401888 -0.249313 H 4.311953 0.267836 -1.651059 C 3.749286 -1.000494 -0.010804 H 4.457423 -1.779698 -0.330663 H 3.798071 -0.996815 1.086609 O 1.077106 2.551715 -1.248778 H -0.286165 1.906624 2.410155 C -1.380930 0.419544 0.453579 H -0.380472 0.086931 0.695668 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.22710519 Predicted Change= -2.173486D-09 Zero-point correction (ZPE)= -1075.8428 0.38427 Internal Energy (U)= -1075.8222 0.40487 Enthalpy (H)= -1075.8212 0.40582 Gibbs Free Energy (G)= -1075.8915 0.33552 ------------------------------------------------------------------------------ Frequencies -- -137.1320 25.1228 40.2174

5.2.40 TSba→bac Supporting Information: 025-TS1-COin-C7-8out-11-12out-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23907853 Predicted Change= -5.129182D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00039 || 0.00180 [ YES ] 0.00039 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.216343 -2.299966 0.635980 H -1.438390 -2.527269 1.673784 C 0.107813 -2.150527 0.221707 O 1.207004 -2.323193 1.006309 C 1.016761 -2.643787 2.376468 H 0.487859 -3.598229 2.495306 H 0.462059 -1.853874 2.899092 H 2.017636 -2.726202 2.802612 C 0.362315 -1.716269 -1.094969 O 1.646539 -1.312550 -1.440446 C 2.053233 -0.134719 -0.791270 C -0.670873 -1.639344 -2.016374 H -0.437387 -1.350418 -3.036633 C -1.992929 -1.829692 -1.598957 H -2.803344 -1.681464 -2.308086 C -2.279604 -2.059641 -0.250513 C 3.328081 -0.175356 -0.209235 O 4.083349 -1.305069 -0.269871 H 3.511531 -1.993172 -0.656431 C 3.798800 0.960676 0.446999 H 4.785535 0.930876 0.898950 C 2.988411 2.093244 0.550215 H 3.364629 2.960950 1.087165 C 1.705412 2.136484 -0.010562 C 0.831811 3.369856 0.147445 H 1.410965 4.133584 0.677291 C -0.498092 3.136219 0.903502 H -0.768439 4.039023 1.474411 H -0.402506 2.337814 1.649914 C -1.701281 2.860829 0.000277 C -2.910961 2.146642 0.604459 H -3.801098 2.485508 0.063336 H -3.033331 2.381853 1.669460 C -2.695454 0.632681 0.390415 H -1.882623 0.293874 1.042665 H -2.336219 0.501504 -0.633712 C -3.928778 -0.266227 0.582271 H -4.719932 0.085422 -0.091422 H -4.322167 -0.150617 1.600079 C -3.664618 -1.802551 0.305406


S51

S51

H -3.793984 -2.362020 1.238702 H -4.428049 -2.173084 -0.387867 O -1.695303 3.160642 -1.180586 H 0.577568 3.789355 -0.833398 C 1.256005 1.001295 -0.705117 H 0.278733 0.998862 -1.177356 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23907853 Predicted Change= -5.129182D-10 Zero-point correction (ZPE)= -1075.8553 0.38375 Internal Energy (U)= -1075.8346 0.40447 Enthalpy (H)= -1075.8336 0.40541 Gibbs Free Energy (G)= -1075.9045 0.33451 ------------------------------------------------------------------------------ Frequencies -- -127.1895 24.4715 44.1719

5.2.41 TSba→bad Supporting Information: 025-TS-COin-C7-8out-Ph-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.16692287 Predicted Change= -2.146880D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00241 || 0.00180 [ NO ] 0.00241 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.816919 2.446624 0.008434 H 2.444031 3.300963 0.242465 C 2.446512 1.220420 -0.334395 O 3.799443 1.032807 -0.382525 C 4.645698 2.131954 -0.089434 H 4.492985 2.499234 0.934245 H 4.492123 2.959165 -0.795190 H 5.666039 1.757236 -0.190100 C 1.657318 0.080707 -0.621582 O 2.189693 -1.198373 -0.911587 C 1.258939 -2.199106 -0.528170 C 0.296026 0.246812 -0.553703 H -0.368739 -0.568775 -0.694420 C -0.295899 1.424409 -0.209686 H -1.355002 1.402886 -0.134929 C 0.411608 2.563101 0.092353 C 1.428506 -2.734633 0.752999 O 2.595387 -2.565809 1.429845 H 3.167289 -2.013351 0.864965 C 0.341885 -3.368949 1.365659 H 0.471052 -3.778090 2.362763 C -0.918246 -3.306386 0.771024 H -1.782181 -3.638892 1.339962 C -1.107705 -2.764972 -0.510350 C -2.505603 -2.382556 -1.004170 H -2.677583 -2.799119 -2.006163 C -2.873381 -0.855815 -1.124970 H -3.838004 -0.802127 -1.651146 H -2.174618 -0.331761 -1.791907 C -3.033260 -0.018197 0.166095 C -3.681639 1.411566 0.084337 H -4.194856 1.509462 1.047520 H -4.457620 1.363728 -0.691693 C -2.907392 2.767501 -0.173634 H -3.710868 3.506628 -0.281744 H -2.419740 2.735582 -1.153983 C -1.912735 3.297152 0.930894 H -1.811811 2.545106 1.722469 H -2.380583 4.168183 1.404449 C -0.469399 3.740276 0.498459 H -0.542591 4.467322 -0.324851 H -0.022994 4.288006 1.338807 O -2.780533 -0.496553 1.255056 H -3.244807 -2.849591 -0.344367

C 0.044999 -2.362481 -1.207651 H -0.042344 -1.922934 -2.198515 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.16692287 Predicted Change= -2.146880D-08 Zero-point correction (ZPE)= -1075.7826 0.38429 Internal Energy (U)= -1075.7623 0.40460 Enthalpy (H)= -1075.7613 0.40555 Gibbs Free Energy (G)= -1075.8301 0.33679 ------------------------------------------------------------------------------ Frequencies -- -146.6739 38.7687 51.8142

5.2.42 TSbc→bca Supporting Information: 025-TS-COout-C11-12out-7-8-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23397647 Predicted Change= -2.294672D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00129 || 0.00180 [ YES ] 0.00129 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -2.425713 -1.422043 0.288137 H -3.198707 -1.433250 1.050025 C -1.169141 -1.974629 0.563269 O -0.809642 -2.556455 1.741521 C -1.798940 -2.692389 2.749484 H -2.652402 -3.286881 2.398407 H -2.160363 -1.715532 3.098350 H -1.310936 -3.211643 3.576058 C -0.159822 -1.869918 -0.412700 O 1.150796 -2.217894 -0.083523 C 1.979674 -1.092550 0.007948 C -0.442423 -1.334794 -1.660622 H 0.354249 -1.281172 -2.396588 C -1.700017 -0.794811 -1.925594 H -1.892483 -0.330061 -2.888256 C -2.681678 -0.774525 -0.932341 C 3.153261 -1.119386 -0.755824 O 3.469818 -2.212413 -1.505958 H 2.757905 -2.861734 -1.360998 C 3.978146 0.005768 -0.753608 H 4.882032 -0.008378 -1.354656 C 3.616447 1.135197 -0.017671 H 4.258741 2.011677 -0.048525 C 2.449528 1.164495 0.756886 C 2.093328 2.370107 1.604260 H 2.015193 2.043242 2.648594 C 0.781176 3.179669 1.277169 H 1.071310 4.203283 1.012810 H 0.175099 3.251565 2.185894 C -0.102800 2.717340 0.109258 C -1.493760 2.181036 0.451566 H -1.873437 2.696689 1.344111 H -1.348081 1.134636 0.760357 C -2.522540 2.256333 -0.687793 H -2.045961 1.916522 -1.612163 H -2.775674 3.311031 -0.851678 C -3.817290 1.451090 -0.402067 H -4.693444 2.038787 -0.703639 H -3.920315 1.298622 0.681062 C -3.921476 0.072058 -1.112626 H -4.811899 -0.447226 -0.734443 H -4.086542 0.239650 -2.183991 O 0.288327 2.802924 -1.039208 H 2.936236 3.067381 1.576293 C 1.647673 0.017347 0.773964 H 0.743281 -0.018890 1.373748 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis


S52

S52

Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23397647 Predicted Change= -2.294672D-09 Zero-point correction (ZPE)= -1075.8504 0.38355 Internal Energy (U)= -1075.8295 0.40442 Enthalpy (H)= -1075.8286 0.40536 Gibbs Free Energy (G)= -1075.9003 0.33359 ------------------------------------------------------------------------------ Frequencies -- -146.3831 20.1955 33.4219

5.2.43 TSbc→bcd Supporting Information: 025-TS-COout-C11-12out-Ph-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.16611635 Predicted Change= -7.224438D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00096 || 0.00180 [ YES ] 0.00096 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 3.060845 0.710164 -0.004851 H 4.104077 0.950531 0.173246 C 2.709666 -0.645020 -0.235576 O 3.604608 -1.677432 -0.288097 C 4.981615 -1.384676 -0.128341 H 5.193957 -0.957537 0.861157 H 5.340104 -0.692672 -0.902242 H 5.502765 -2.338866 -0.227590 C 1.347749 -1.003429 -0.395816 O 0.917833 -2.331199 -0.624370 C -0.484498 -2.448027 -0.485059 C 0.431234 0.018293 -0.330701 H -0.616967 -0.162658 -0.321259 C 0.799328 1.329289 -0.235738 H 0.015278 2.039915 -0.299864 C 2.089153 1.737000 -0.006310 C -0.958527 -3.045460 0.686373 O -0.128557 -3.750686 1.499212 H 0.763880 -3.681715 1.112464 C -2.297496 -2.843378 1.052358 H -2.661868 -3.312965 1.960663 C -3.081899 -1.926611 0.353365 H -4.058497 -1.664233 0.753241 C -2.608709 -1.296624 -0.810039 C -3.248766 -0.044011 -1.408125 H -2.673578 0.243092 -2.296108 C -3.421664 1.236546 -0.489230 H -4.184946 0.998468 0.261212 H -3.844648 2.014134 -1.138146 C -2.261411 1.844252 0.349145 C -1.680773 3.236059 -0.044217 H -2.525524 3.932516 0.072250 H -1.477216 3.240436 -1.124695 C -0.449089 3.762017 0.789855 H -0.281909 3.056247 1.609997 H -0.761027 4.699853 1.262084 C 0.904967 4.052986 0.017182 H 1.173344 5.098016 0.211048 H 0.720392 3.997479 -1.064382 C 2.203487 3.221015 0.325524 H 3.030342 3.696673 -0.220442 H 2.451319 3.333426 1.391730 O -1.903738 1.281525 1.364789 H -4.266339 -0.253278 -1.765727 C -1.355434 -1.706877 -1.290362 H -0.942763 -1.235574 -2.177533 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.16611635 Predicted Change= -7.224438D-09


5.2.44 TSbd→bda Supporting Information: 025-TS-COin-Ph-C7-8-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23291429 Predicted Change= -8.248019D-11 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00028 || 0.00180 [ YES ] 0.00028 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.320739 -2.036727 0.635647 H 1.615575 -2.092975 1.678401 C -0.029086 -2.041639 0.299271 O -1.058315 -2.149672 1.182433 C -0.796518 -1.865100 2.554111 H -0.304566 -0.891554 2.658617 H -0.181226 -2.647970 3.016248 H -1.773101 -1.842234 3.040336 C -0.395829 -1.848758 -1.047652 O -1.727508 -1.563102 -1.342238 C -2.101057 -0.309850 -0.827435 C 0.570920 -1.814371 -2.039884 H 0.255861 -1.690396 -3.071773 C 1.927782 -1.823877 -1.689321 H 2.682404 -1.720882 -2.464868 C 2.308459 -1.855961 -0.346105 C -3.259510 -0.275032 -0.038432 O -3.975625 -1.407434 0.195886 H -3.429424 -2.145399 -0.131677 C -3.648676 0.941804 0.520773 H -4.544722 0.971003 1.133202 C -2.867550 2.083384 0.326483 H -3.177516 3.017942 0.788373 C -1.696451 2.048376 -0.439006 C -0.890325 3.306291 -0.702670 H -0.840606 3.447150 -1.790065 C 0.579639 3.456229 -0.176049 H 0.607692 4.273671 0.562358 H 1.212368 3.810254 -0.996893 C 1.321478 2.322498 0.540589 C 2.854427 2.343007 0.409983 H 3.273369 2.442157 1.420002 H 3.170072 3.226120 -0.155036 C 3.411432 1.056468 -0.259232 H 4.326034 1.312274 -0.809125 H 2.693637 0.706426 -1.010313 C 3.715871 -0.080748 0.735109 H 2.967005 -0.059545 1.533746 H 4.690037 0.103640 1.208744 C 3.709945 -1.496654 0.100122 H 4.404737 -1.534729 -0.748698 H 4.078490 -2.215348 0.843943 O 0.763132 1.490516 1.231038 H -1.465200 4.159785 -0.328083 C -1.340930 0.832186 -1.035206 H -0.442958 0.758983 -1.640970 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23291429 Predicted Change= -8.248019D-11 Zero-point correction (ZPE)= -1075.8493 0.38356 Internal Energy (U)= -1075.8285 0.40432 Enthalpy (H)= -1075.8276 0.40526 Gibbs Free Energy (G)= -1075.8986 0.33423


S53

S53

------------------------------------------------------------------------------ Frequencies -- -170.5252 26.5307 38.2576

5.2.45 TSbd→bdc Supporting Information: 025-TS-COout-Ph-C11-12in-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.22308095 Predicted Change= -9.075460D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00069 || 0.00180 [ YES ] 0.00069 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -0.406042 -2.611191 0.591946 H -0.200654 -2.846088 1.631327 C -1.528755 -1.852704 0.260564 O -2.468320 -1.403551 1.139281 C -2.270497 -1.650276 2.525908 H -1.331636 -1.206067 2.878591 H -2.272076 -2.725731 2.744398 H -3.111020 -1.174279 3.032966 C -1.663512 -1.386491 -1.062442 O -2.493965 -0.289576 -1.301688 C -1.885173 0.890611 -0.831689 C -0.839577 -1.877133 -2.063192 H -1.002814 -1.543986 -3.084082 C 0.283156 -2.640035 -1.721401 H 1.007410 -2.897050 -2.490151 C 0.573107 -2.892327 -0.378231 C -2.639640 1.674419 0.049045 O -3.890160 1.296554 0.422518 H -4.002150 0.381118 0.104873 C -2.073768 2.850843 0.551488 H -2.663138 3.459886 1.230071 C -0.769373 3.206264 0.211852 H -0.349125 4.119344 0.627415 C 0.006966 2.408529 -0.642912 C 1.425346 2.794265 -1.030934 H 1.760965 2.151932 -1.853937 C 2.490696 2.782592 0.103205 H 2.141071 3.381058 0.950052 H 3.395658 3.265343 -0.294874 C 2.906230 1.422268 0.671108 C 3.688436 0.471006 -0.240793 H 4.690659 0.908676 -0.372556 H 3.233833 0.483657 -1.241064 C 3.784479 -0.979901 0.271369 H 4.403086 -1.013180 1.174716 H 4.306871 -1.572449 -0.490953 C 2.377874 -1.554217 0.546420 H 1.662927 -0.888047 0.054558 H 2.146978 -1.464347 1.611514 C 2.020861 -3.000330 0.065139 H 2.654376 -3.301009 -0.778281 H 2.174994 -3.732257 0.867324 O 2.673055 1.137134 1.831898 H 1.419371 3.815085 -1.435895 C -0.582875 1.253532 -1.169865 H -0.018101 0.615558 -1.841588 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.22308095 Predicted Change= -9.075460D-10 Zero-point correction (ZPE)= -1075.8396 0.38344 Internal Energy (U)= -1075.8190 0.40400 Enthalpy (H)= -1075.8181 0.40494 Gibbs Free Energy (G)= -1075.8881 0.33493 ------------------------------------------------------------------------------ Frequencies -- -79.9814 31.0409 46.1594

5.2.46 TSca→cab Supporting Information: 025-TS-C11-12in-7-8-COin-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23926205 Predicted Change= -5.046406D-11 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00035 || 0.00180 [ YES ] 0.00035 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -0.976257 -2.232396 0.686160 H -1.286742 -2.361185 1.718119 C 0.374246 -2.067327 0.379061 O 1.396063 -2.068877 1.278321 C 1.081902 -2.207264 2.656953 H 0.598272 -3.170671 2.863207 H 0.432308 -1.393096 3.002791 H 2.035852 -2.159124 3.184070 C 0.742201 -1.811465 -0.958750 O 2.036384 -1.369059 -1.227115 C 2.223865 -0.049311 -0.788456 C -0.203046 -1.874598 -1.968951 H 0.116969 -1.701251 -2.992150 C -1.554255 -2.057201 -1.650525 H -2.298264 -2.044236 -2.442274 C -1.958466 -2.159925 -0.318357 C 3.403334 0.216810 -0.082628 O 4.318144 -0.764661 0.139754 H 3.904609 -1.596361 -0.155702 C 3.610209 1.509659 0.403867 H 4.527277 1.719416 0.945911 C 2.630696 2.490970 0.235336 H 2.799162 3.480832 0.653356 C 1.435154 2.220624 -0.445486 C 0.318057 3.244016 -0.534918 H 0.756949 4.247795 -0.530697 C -0.719464 3.186677 0.637872 H -0.930244 4.197041 0.999757 H -0.272043 2.634391 1.476135 C -2.098278 2.567815 0.366472 C -2.175103 1.164707 -0.243450 H -1.451086 0.527693 0.277235 H -1.781239 1.248624 -1.265229 C -3.593152 0.547010 -0.255065 H -3.869957 0.276251 -1.281902 H -4.288245 1.335797 0.050620 C -3.809149 -0.679289 0.659370 H -4.874261 -0.735482 0.919776 H -3.276440 -0.526802 1.608395 C -3.417686 -2.059561 0.066038 H -3.672010 -2.832578 0.803883 H -4.041506 -2.252688 -0.815975 O -3.100581 3.192475 0.664685 H -0.201478 3.150693 -1.496645 C 1.269182 0.940433 -0.983882 H 0.368102 0.693623 -1.531791 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23926205 Predicted Change= -5.046406D-11 Zero-point correction (ZPE)= -1075.8555 0.38370 Internal Energy (U)= -1075.8349 0.40431 Enthalpy (H)= -1075.8340 0.40526 Gibbs Free Energy (G)= -1075.9046 0.33464 ------------------------------------------------------------------------------ Frequencies -- -30.2816 20.5575 41.7800

5.2.47 TSca→cad


S54

S54

5.2.48 TScb→cba Supporting Information: 025-TS-C11-12in-7-8-Ph-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.14964814 Predicted Change= -5.210037D-09 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00201 || 0.00180 [ NO ] 0.00201 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -2.853738 1.252738 -0.076335 H -3.821168 1.689582 -0.302215 C -2.784180 -0.145411 0.166735 O -3.862438 -0.983718 0.168404 C -5.148936 -0.431952 -0.056224 H -5.225138 0.026825 -1.051225 H -5.405767 0.316192 0.705476 H -5.847052 -1.268561 0.009007 C -1.527906 -0.758162 0.400684 O -1.361710 -2.135764 0.666173 C -0.001085 -2.512257 0.522055 C -0.432174 0.070955 0.382850 H 0.555140 -0.313309 0.456139 C -0.529997 1.426363 0.276620 H 0.369808 1.980013 0.405874 C -1.704580 2.072326 -0.017815 C 0.341754 -3.134837 -0.682952 O -0.614503 -3.651650 -1.499723 H -1.473330 -3.457509 -1.081041 C 1.684814 -3.141711 -1.078793 H 1.949524 -3.625434 -2.013853 C 2.619950 -2.388394 -0.368382 H 3.611623 -2.249734 -0.789118 C 2.289089 -1.744921 0.836044 C 3.163665 -0.619090 1.394387 H 3.247382 -0.706263 2.485506 C 2.679652 0.860713 1.121107 H 3.390843 1.523396 1.640153 H 1.717151 1.055574 1.599355 C 2.706436 1.326121 -0.352208 C 1.898359 2.509268 -1.040684 H 1.146807 1.981782 -1.640753 H 2.643474 2.843148 -1.771587 C 1.267941 3.848783 -0.486949 H 1.235868 4.473994 -1.389134 H 2.009072 4.334111 0.162750 C -0.121052 4.088108 0.234152 H -0.203577 5.182670 0.246547 H -0.046106 3.796682 1.288933 C -1.497011 3.555714 -0.303650 H -2.286295 4.168063 0.152926 H -1.567661 3.739443 -1.386356 O 3.446908 0.733055 -1.116112 H 4.173905 -0.716163 0.986784 C 0.995358 -1.967511 1.342488 H 0.681291 -1.470945 2.257115 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.14964814 Predicted Change= -5.210037D-09 Zero-point correction (ZPE)= -1075.7647 0.38485 Internal Energy (U)= -1075.7446 0.40501 Enthalpy (H)= -1075.7436 0.40595 Gibbs Free Energy (G)= -1075.8123 0.33734 ------------------------------------------------------------------------------ Frequencies -- -121.2470 27.6788 59.7212

5.2.49 TScb→cbd Supporting Information: 025-TS-C11-12in-Coin-C7-8-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23397647 Predicted Change= -2.310118D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00127 || 0.00180 [ YES ] 0.00127 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -2.425708 -1.422051 0.288138 H -3.198701 -1.433261 1.050027 C -1.169133 -1.974632 0.563269 O -0.809630 -2.556457 1.741520 C -1.798926 -2.692396 2.749484 H -2.652386 -3.286891 2.398408 H -2.160353 -1.715541 3.098351 H -1.310918 -3.211649 3.576057 C -0.159815 -1.869918 -0.412703 O 1.150804 -2.217891 -0.083527 C 1.979679 -1.092544 0.007946 C -0.442419 -1.334794 -1.660624 H 0.354251 -1.281169 -2.396590 C -1.700016 -0.794816 -1.925594 H -1.892484 -0.330066 -2.888255 C -2.681676 -0.774535 -0.932340 C 3.153270 -1.119377 -0.755821 O 3.469834 -2.212405 -1.505952 H 2.757920 -2.861726 -1.360998 C 3.978151 0.005779 -0.753604 H 4.882040 -0.008365 -1.354647 C 3.616446 1.135208 -0.017669 H 4.258738 2.011690 -0.048520 C 2.449523 1.164503 0.756883 C 2.093317 2.370113 1.604258 H 2.015178 2.043244 2.648591 C 0.781166 3.179675 1.277163 H 1.071300 4.203288 1.012798 H 0.175091 3.251577 2.185889 C -0.102815 2.717343 0.109257 C -1.493773 2.181039 0.451570 H -1.873452 2.696700 1.344110 H -1.348090 1.134642 0.760372 C -2.522552 2.256323 -0.687791 H -2.045970 1.916511 -1.612159 H -2.775692 3.311019 -0.851681 C -3.817297 1.451074 -0.402063 H -4.693456 2.038766 -0.703631 H -3.920318 1.298603 0.681067 C -3.921478 0.072043 -1.112624 H -4.811899 -0.447246 -0.734441 H -4.086545 0.239636 -2.183988 O 0.288309 2.802925 -1.039211 H 2.936225 3.067388 1.576297 C 1.647672 0.017353 0.773958 H 0.743277 -0.018885 1.373738 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23397647 Predicted Change= -2.310118D-09 Zero-point correction (ZPE)= -1075.8504 0.38355 Internal Energy (U)= -1075.8295 0.40442 Enthalpy (H)= -1075.8286 0.40536 Gibbs Free Energy (G)= -1075.9003 0.33359 ------------------------------------------------------------------------------ Frequencies -- -146.3820 20.1957 33.4232

5.2.50 TScd→cda Supporting Information: 025-TS-C11-12in-Coin-Ph-Galeon.log


S55

S55

------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.16611638 Predicted Change= -6.813671D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00102 || 0.00180 [ YES ] 0.00102 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 3.060667 0.710975 -0.004978 H 4.103849 0.951608 0.173045 C 2.709826 -0.644291 -0.235720 O 3.605021 -1.676484 -0.288193 C 4.981935 -1.383437 -0.128155 H 5.193957 -0.956133 0.861340 H 5.340465 -0.691458 -0.902059 H 5.503299 -2.337535 -0.227172 C 1.347997 -1.003075 -0.395968 O 0.918457 -2.331007 -0.624333 C -0.483849 -2.448242 -0.485025 C 0.431236 0.018408 -0.331033 H -0.616920 -0.162799 -0.321777 C 0.798975 1.329483 -0.235791 H 0.014724 2.039891 -0.299688 C 2.088694 1.737550 -0.006385 C -0.957713 -3.045637 0.686497 O -0.127575 -3.750577 1.499411 H 0.764857 -3.681400 1.112689 C -2.296711 -2.843781 1.052507 H -2.660938 -3.313311 1.960900 C -3.081328 -1.927239 0.353457 H -4.057943 -1.664990 0.753377 C -2.608338 -1.297324 -0.810065 C -3.248570 -0.044829 -1.408236 H -2.673199 0.242469 -2.296038 C -3.422000 1.235640 -0.489333 H -4.185266 0.997327 0.261050 H -3.845165 2.013100 -1.138283 C -2.261958 1.843636 0.349107 C -1.681691 3.235638 -0.044111 H -2.526599 3.931921 0.072216 H -1.477976 3.240006 -1.124557 C -0.450171 3.761817 0.790070 H -0.282784 3.055973 1.610108 H -0.762364 4.699494 1.262449 C 0.903790 4.053235 0.017386 H 1.171895 5.098313 0.211377 H 0.719162 3.997817 -1.064173 C 2.202613 3.221605 0.325501 H 3.029177 3.697546 -0.220659 H 2.450672 3.334084 1.391644 O -1.904012 1.280837 1.364616 H -4.265990 -0.254307 -1.766156 C -1.355001 -1.707406 -1.290393 H -0.942467 -1.236133 -2.177643 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.16611638 Predicted Change= -6.813671D-09 Zero-point correction (ZPE)= -1075.7817 0.38434 Internal Energy (U)= -1075.7615 0.40460 Enthalpy (H)= -1075.7605 0.40554 Gibbs Free Energy (G)= -1075.8287 0.33731 ------------------------------------------------------------------------------ Frequencies -- -129.4273 50.2657 55.2400

5.2.51 TScd→cdb Supporting Information: 025-TS-C11-12out-Ph-C7-8-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ==============================================================================

# b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23133700 Predicted Change= -4.923440D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00087 || 0.00180 [ YES ] 0.00087 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.070488 -2.275368 -0.435906 H -1.247780 -2.678183 -1.427819 C 0.234883 -2.134078 0.039867 O 1.365550 -2.494837 -0.632864 C 1.237717 -2.997980 -1.954873 H 0.750749 -2.268587 -2.614517 H 0.672566 -3.938694 -1.972610 H 2.256449 -3.177120 -2.301820 C 0.441694 -1.495364 1.277199 O 1.726440 -1.053204 1.600967 C 2.055296 0.078829 0.834416 C -0.635647 -1.185005 2.093194 H -0.443784 -0.727098 3.058750 C -1.937817 -1.350013 1.617865 H -2.772315 -1.015038 2.226179 C -2.160177 -1.806711 0.315830 C 3.197569 -0.015291 0.029213 O 3.966026 -1.135650 0.028872 H 3.454423 -1.814466 0.506913 C 3.512943 1.060318 -0.803907 H 4.390824 0.987127 -1.438588 C 2.673710 2.172125 -0.858081 H 2.918909 2.980819 -1.542851 C 1.522733 2.270852 -0.060575 C 0.677398 3.534075 -0.127765 H 1.011812 4.209652 0.670897 C -0.892099 3.480262 -0.018804 H -1.303341 3.994950 -0.898740 H -1.208105 4.051270 0.857847 C -1.656491 2.155106 0.088896 C -1.671648 1.193645 -1.096200 H -1.024267 0.353123 -0.826041 H -1.198633 1.675013 -1.961042 C -3.071741 0.676893 -1.525951 H -2.928895 0.099245 -2.450546 H -3.673701 1.549385 -1.814628 C -3.918469 -0.158263 -0.537799 H -4.948780 -0.158088 -0.919715 H -3.941776 0.351309 0.428893 C -3.520176 -1.643277 -0.327015 H -4.294614 -2.106780 0.299242 H -3.543302 -2.169554 -1.290623 O -2.288446 1.917546 1.106620 H 0.937481 4.047213 -1.059654 C 1.247876 1.213027 0.814019 H 0.377138 1.240962 1.459977 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23133700 Predicted Change= -4.923440D-09 Zero-point correction (ZPE)= -1075.8472 0.38404 Internal Energy (U)= -1075.8267 0.40458 Enthalpy (H)= -1075.8258 0.40553 Gibbs Free Energy (G)= -1075.8953 0.33600 ------------------------------------------------------------------------------ Frequencies -- -157.0188 35.4629 55.8096

5.2.52 TSda→dab Supporting Information: 025-TS2-C11-12out-Ph-COin-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------


S56

S56

Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24133994 Predicted Change= -1.045688D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00137 || 0.00180 [ YES ] 0.00137 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.206336 -2.029425 0.798595 H 1.598444 -1.960318 1.807805 C -0.173601 -2.005901 0.580826 O -1.123801 -1.915135 1.550460 C -0.700115 -1.804186 2.902141 H -0.093304 -0.903305 3.058927 H -0.128662 -2.686734 3.216903 H -1.613925 -1.733309 3.493883 C -0.650094 -1.999335 -0.744810 O -1.984276 -1.674167 -0.979692 C -2.230690 -0.316302 -0.733539 C 0.224255 -2.171738 -1.807224 H -0.180477 -2.190421 -2.814807 C 1.601686 -2.215609 -1.575524 H 2.285156 -2.291282 -2.417226 C 2.104650 -2.064850 -0.279603 C -3.432763 -0.009761 -0.085668 O -4.308154 -0.992827 0.259190 H -3.858214 -1.838031 0.077880 C -3.707206 1.326826 0.212705 H -4.642579 1.565598 0.709585 C -2.772958 2.321062 -0.084815 H -2.996073 3.351108 0.184296 C -1.554879 2.014432 -0.708706 C -0.491940 3.071611 -0.944414 H 0.127721 2.794149 -1.805815 C 0.408375 3.378974 0.287864 H -0.154858 3.148709 1.203877 H 0.621016 4.452044 0.339662 C 1.784219 2.711589 0.468470 C 2.101930 1.350057 -0.150478 H 2.073243 1.464271 -1.245524 H 1.284349 0.659752 0.085448 C 3.471308 0.807827 0.295607 H 3.430110 0.568701 1.366766 H 4.185523 1.634053 0.217760 C 4.039414 -0.397105 -0.486961 H 5.132305 -0.377491 -0.381342 H 3.839319 -0.268666 -1.559972 C 3.578635 -1.814118 -0.054658 H 4.172984 -2.546074 -0.617683 H 3.825996 -1.960376 1.004643 O 2.609039 3.292626 1.152557 H -0.984785 4.010578 -1.223217 C -1.318166 0.681558 -1.057240 H -0.396129 0.409431 -1.557385 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24133994 Predicted Change= -1.045688D-09 Zero-point correction (ZPE)= -1075.8577 0.38355 Internal Energy (U)= -1075.8371 0.40416 Enthalpy (H)= -1075.8362 0.40511 Gibbs Free Energy (G)= -1075.9065 0.33483 ------------------------------------------------------------------------------ Frequencies -- -37.7405 25.0466 41.3042

5.2.53 TSda→dac Supporting Information: 025-TS3-Ph-C7-8in-COin-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24059621 Predicted Change= -2.905810D-09

============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00113 || 0.00180 [ YES ] 0.00113 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.293688 -2.130527 -0.536906 H -1.589446 -2.328065 -1.561961 C 0.057836 -2.089262 -0.200671 O 1.093191 -2.315141 -1.053982 C 0.803929 -2.523384 -2.430178 H 0.275300 -1.663609 -2.860129 H 0.207262 -3.432140 -2.580896 H 1.771579 -2.637991 -2.920558 C 0.421898 -1.720602 1.111776 O 1.752128 -1.409426 1.377935 C 2.147451 -0.212381 0.755746 C -0.548645 -1.578656 2.090792 H -0.235958 -1.333364 3.101460 C -1.904946 -1.646082 1.745539 H -2.660020 -1.453638 2.503052 C -2.285221 -1.830122 0.415448 C 3.336787 -0.250570 0.023077 O 4.063603 -1.396068 -0.074978 H 3.516266 -2.100150 0.318180 C 3.750775 0.913350 -0.631339 H 4.671814 0.886004 -1.205680 C 2.963250 2.062385 -0.586161 H 3.289261 2.945331 -1.131483 C 1.755334 2.101628 0.128919 C 0.921306 3.376921 0.136335 H 1.457084 4.149308 0.705761 C -0.504945 3.273290 0.711552 H -0.878631 4.295300 0.861856 H -0.499506 2.799682 1.698738 C -1.529955 2.603261 -0.217546 C -2.304600 1.414147 0.342223 H -2.437914 1.552642 1.421600 H -1.597330 0.580314 0.256499 C -3.643915 1.082507 -0.355871 H -3.794566 1.816810 -1.155732 H -4.461594 1.230292 0.361754 C -3.793063 -0.315764 -0.991610 H -3.053258 -0.422962 -1.795790 H -4.775685 -0.344809 -1.481344 C -3.698120 -1.556608 -0.060174 H -4.364790 -1.425060 0.801601 H -4.079955 -2.422019 -0.619418 O -1.688014 3.010438 -1.353888 H 0.839254 3.760252 -0.888175 C 1.377104 0.945502 0.817969 H 0.462145 0.915259 1.396454 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24059621 Predicted Change= -2.905810D-09 Zero-point correction (ZPE)= -1075.8565 0.38402 Internal Energy (U)= -1075.8361 0.40448 Enthalpy (H)= -1075.8351 0.40543 Gibbs Free Energy (G)= -1075.9050 0.33559 ------------------------------------------------------------------------------ Frequencies -- -64.6392 26.5675 44.5554

5.2.54 TSdb→dba Supporting Information: 025-TS2-Ph-C7-8in-11-12in-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.22710512 Predicted Change= -9.858530D-09 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass?


S57

S57

Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00320 || 0.00180 [ NO ] 0.00320 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.575950 -2.191889 0.445954 H 2.049125 -2.592051 1.337063 C 0.207211 -2.390233 0.238771 O -0.622842 -3.069156 1.075540 C -0.062223 -3.676386 2.229106 H 0.375343 -2.930706 2.906195 H 0.704235 -4.415777 1.962595 H -0.890401 -4.178075 2.732306 C -0.400803 -1.751020 -0.858629 O -1.787111 -1.605615 -0.876085 C -2.197065 -0.388314 -0.327764 C 0.369546 -1.075544 -1.791964 H -0.131294 -0.583588 -2.620033 C 1.739993 -0.904369 -1.587149 H 2.299990 -0.293964 -2.286246 C 2.338232 -1.389290 -0.421825 C -3.505541 0.013758 -0.634089 O -4.318399 -0.774677 -1.394419 H -3.801099 -1.559833 -1.645381 C -3.958430 1.243044 -0.155005 H -4.970782 1.549771 -0.399602 C -3.118276 2.064897 0.603846 H -3.489499 3.026743 0.949637 C -1.815330 1.664640 0.916775 C -0.843221 2.527524 1.696352 H -1.396484 3.260327 2.295765 C 0.162744 3.325226 0.817639 H 0.747979 3.976273 1.483708 H -0.393164 3.961583 0.122595 C 1.153253 2.524837 -0.033408 C 2.272858 1.727115 0.659830 H 1.873669 0.717890 0.814741 H 2.448557 2.133450 1.663144 C 3.582603 1.695618 -0.177359 H 4.320634 2.309078 0.351086 H 3.365490 2.220196 -1.111247 C 4.277150 0.341796 -0.558575 H 5.328000 0.403834 -0.250728 H 4.311022 0.269508 -1.651996 C 3.749654 -0.999280 -0.011678 H 4.457990 -1.778097 -0.332036 H 3.798912 -0.995814 1.085716 O 1.075532 2.552159 -1.248356 H -0.286822 1.906119 2.410686 C -1.381281 0.418765 0.454422 H -0.380983 0.086086 0.697110 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.22710512 Predicted Change= -9.858530D-09 Zero-point correction (ZPE)= -1075.8428 0.38427 Internal Energy (U)= -1075.8222 0.40487 Enthalpy (H)= -1075.8212 0.40582 Gibbs Free Energy (G)= -1075.8915 0.33552 ------------------------------------------------------------------------------ Frequencies -- -137.1870 25.1529 40.2013

5.2.55 TSdb→dbc Supporting Information: 025-TS-Ph-COin-C7-8-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23232465 Predicted Change= -1.874851D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00123 || 0.00180 [ YES ] 0.00123 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms)

Type X Y Z ------------------------------------------------------------------------------ C 1.376069 -1.868821 0.653718 H 1.651445 -1.903414 1.702160 C 0.035108 -1.937712 0.291246 O -1.003116 -2.086976 1.156324 C -0.772950 -1.804484 2.534637 H -0.317126 -0.815307 2.655780 H -0.136836 -2.568815 2.999282 H -1.756933 -1.821128 3.005753 C -0.312428 -1.770490 -1.064878 O -1.648744 -1.545215 -1.391784 C -2.110395 -0.340670 -0.836777 C 0.672449 -1.708585 -2.038406 H 0.373660 -1.609251 -3.077807 C 2.021685 -1.667815 -1.661150 H 2.788254 -1.551445 -2.423100 C 2.375467 -1.661761 -0.309721 C -3.296451 -0.408241 -0.093794 O -3.963705 -1.584445 0.046085 H -3.376387 -2.274472 -0.313067 C -3.758806 0.750324 0.529840 H -4.671617 0.698307 1.115354 C -3.020623 1.932119 0.444810 H -3.381180 2.815798 0.965873 C -1.827365 2.003646 -0.285548 C -1.085686 3.320149 -0.415853 H -1.239408 3.698972 -1.435064 C 0.463483 3.398037 -0.145344 H 0.623496 4.122240 0.664189 H 0.950002 3.821281 -1.028281 C 1.246991 2.155637 0.313682 C 2.418435 1.711376 -0.568045 H 2.643605 2.507598 -1.286603 H 2.052806 0.864266 -1.162955 C 3.736155 1.330003 0.149421 H 4.006932 2.156285 0.820627 H 4.519752 1.305443 -0.621309 C 3.818942 0.023234 0.962150 H 3.034193 0.023678 1.724849 H 4.777334 0.047114 1.498737 C 3.769536 -1.307111 0.163623 H 4.456398 -1.252826 -0.691164 H 4.152458 -2.103216 0.817123 O 0.967603 1.587224 1.354638 H -1.579899 4.045109 0.238264 C -1.399702 0.847287 -0.949306 H -0.486732 0.852345 -1.536580 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23232465 Predicted Change= -1.874851D-09 Zero-point correction (ZPE)= -1075.8484 0.38388 Internal Energy (U)= -1075.8277 0.40454 Enthalpy (H)= -1075.8268 0.40548 Gibbs Free Energy (G)= -1075.8971 0.33513 ------------------------------------------------------------------------------ Frequencies -- -172.8428 27.2758 48.1879

5.2.56 TSdc→dca Supporting Information: 025-TS-Ph-COout-C11-12out-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.22308099 Predicted Change= -4.889530D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00041 || 0.00180 [ YES ] 0.00041 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -0.406334 -2.611153 0.591986 H -0.201024 -2.846057 1.631381


S58

S58

C -1.528957 -1.852567 0.260528 O -2.468548 -1.403335 1.139176 C -2.270882 -1.650109 2.525813 H -1.332001 -1.206019 2.878592 H -2.272606 -2.725568 2.744284 H -3.111393 -1.174019 3.032803 C -1.663592 -1.386343 -1.062485 O -2.493941 -0.289356 -1.301772 C -1.885070 0.890771 -0.831723 C -0.839645 -1.877073 -2.063185 H -1.002791 -1.543918 -3.084086 C 0.282995 -2.640086 -1.721322 H 1.007269 -2.897178 -2.490027 C 0.572845 -2.892389 -0.378131 C -2.639484 1.674616 0.049025 O -3.890047 1.296862 0.422467 H -4.002117 0.381436 0.104821 C -2.073514 2.850973 0.551519 H -2.662840 3.460043 1.230117 C -0.769085 3.206293 0.211911 H -0.348761 4.119321 0.627513 C 0.007191 2.408526 -0.642880 C 1.425608 2.794154 -1.030874 H 1.761185 2.151812 -1.853886 C 2.490943 2.782381 0.103277 H 2.141326 3.380811 0.950152 H 3.395927 3.265134 -0.294757 C 2.906434 1.422016 0.671120 C 3.688529 0.470730 -0.240837 H 4.690812 0.908271 -0.372563 H 3.233941 0.483503 -1.241113 C 3.784370 -0.980221 0.271255 H 4.403041 -1.013678 1.174553 H 4.306595 -1.572810 -0.491151 C 2.377697 -1.554312 0.546371 H 1.662848 -0.888159 0.054339 H 2.146760 -1.464201 1.611435 C 2.020563 -3.000478 0.065338 H 2.654109 -3.301394 -0.777976 H 2.174547 -3.732260 0.867682 O 2.673319 1.136877 1.831922 H 1.419712 3.814982 -1.435817 C -0.582741 1.253598 -1.169876 H -0.018013 0.615597 -1.841613 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.22308099 Predicted Change= -4.889530D-10 Zero-point correction (ZPE)= -1075.8396 0.38344 Internal Energy (U)= -1075.8190 0.40400 Enthalpy (H)= -1075.8181 0.40494 Gibbs Free Energy (G)= -1075.8881 0.33493 ------------------------------------------------------------------------------ Frequencies -- -79.9216 31.0487 46.1511

5.2.57 TSdc→dcb Supporting Information: 025-TS-Ph-C11-12in-7-8out-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23133707 Predicted Change= -2.462435D-11 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00006 || 0.00180 [ YES ] 0.00006 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.070622 -2.275485 -0.435585 H -1.247882 -2.678485 -1.427431 C 0.234724 -2.134164 0.040232 O 1.365421 -2.495096 -0.632363 C 1.237660 -2.998436 -1.954304 H 0.750779 -2.269120 -2.614097

H 0.672466 -3.939127 -1.971943 H 2.256408 -3.177680 -2.301150 C 0.441491 -1.495208 1.277441 O 1.726247 -1.053095 1.601180 C 2.055200 0.078841 0.834525 C -0.635875 -1.184614 2.093315 H -0.444030 -0.726523 3.058788 C -1.938025 -1.349621 1.617935 H -2.772545 -1.014448 2.226109 C -2.160318 -1.806602 0.315985 C 3.197497 -0.015465 0.029383 O 3.965820 -1.135914 0.029148 H 3.454107 -1.814651 0.507183 C 3.513043 1.060060 -0.803773 H 4.390969 0.986749 -1.438380 C 2.673949 2.171961 -0.858045 H 2.919306 2.980598 -1.542825 C 1.522895 2.270848 -0.060665 C 0.677626 3.534099 -0.128145 H 1.011832 4.209707 0.670581 C -0.891873 3.480412 -0.019679 H -1.302798 3.994785 -0.899943 H -1.208052 4.051800 0.856670 C -1.656340 2.155316 0.088358 C -1.671365 1.193422 -1.096387 H -1.024206 0.352881 -0.825755 H -1.198075 1.674383 -1.961302 C -3.071472 0.676769 -1.526225 H -2.928587 0.098993 -2.450735 H -3.673320 1.549284 -1.815064 C -3.918403 -0.158183 -0.538065 H -4.948659 -0.157992 -0.920130 H -3.941822 0.351537 0.428552 C -3.520252 -1.643195 -0.326992 H -4.294774 -2.106533 0.299281 H -3.543339 -2.169639 -1.290511 O -2.288395 1.918096 1.106098 H 0.937964 4.047165 -1.060009 C 1.247868 1.213113 0.813985 H 0.377066 1.241169 1.459851 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23133707 Predicted Change= -2.462435D-11 Zero-point correction (ZPE)= -1075.8472 0.38404 Internal Energy (U)= -1075.8267 0.40458 Enthalpy (H)= -1075.8258 0.40553 Gibbs Free Energy (G)= -1075.8953 0.33600 ------------------------------------------------------------------------------ Frequencies -- -157.0995 35.4677 55.8097

5.2.58 TSd→dc Supporting Information: 025-TS1-Ph-C11-12-COin-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24016183 Predicted Change= -1.140286D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00289 || 0.00180 [ NO ] 0.00289 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.178142 -2.166087 0.647522 H 1.473646 -2.304509 1.682229 C -0.175353 -2.087815 0.310836 O -1.215111 -2.200338 1.183006 C -0.924707 -2.394383 2.559930 H -0.348946 -1.554968 2.970316 H -0.372871 -3.328530 2.725483 H -1.892159 -2.449100 3.061193 C -0.527707 -1.797227 -1.021083 O -1.844253 -1.448307 -1.311703


S59

S59

C -2.168015 -0.176728 -0.815183 C 0.443270 -1.753646 -2.010604 H 0.133719 -1.566286 -3.034495 C 1.793149 -1.858171 -1.665765 H 2.551636 -1.759899 -2.437926 C 2.172668 -1.980284 -0.324757 C -3.380021 -0.074347 -0.120538 O -4.180296 -1.161128 0.043699 H -3.669698 -1.926994 -0.277308 C -3.740603 1.164088 0.413142 H -4.682817 1.246506 0.946216 C -2.877523 2.255092 0.296891 H -3.164008 3.203378 0.745934 C -1.649719 2.151747 -0.372393 C -0.678546 3.314587 -0.412157 H -0.182997 3.380227 -1.388659 C 0.417725 3.295734 0.707330 H 0.004659 2.829582 1.608615 H 0.674774 4.333176 0.945370 C 1.745612 2.640587 0.309403 C 1.974296 1.155639 0.601997 H 1.574995 0.627523 -0.273595 H 1.338280 0.839993 1.434860 C 3.461505 0.777086 0.828641 H 3.597920 0.465737 1.873071 H 4.053622 1.688725 0.694357 C 4.077816 -0.291470 -0.098051 H 5.164932 -0.273071 0.058204 H 3.917497 0.007599 -1.142490 C 3.614718 -1.761639 0.079631 H 4.274208 -2.395762 -0.528043 H 3.763741 -2.066870 1.123583 O 2.594997 3.304681 -0.259505 H -1.243872 4.245722 -0.295481 C -1.325412 0.919974 -0.953732 H -0.396708 0.802140 -1.501773 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24016183 Predicted Change= -1.140286D-08 Zero-point correction (ZPE)= -1075.8564 0.38372 Internal Energy (U)= -1075.8357 0.40440 Enthalpy (H)= -1075.8348 0.40535 Gibbs Free Energy (G)= -1075.9064 0.33368 ------------------------------------------------------------------------------ Frequencies -- -64.2369 12.9550 29.0980

5.2.59 Intabc Supporting Information: 030-GS-C7-8-COin-C11-12out-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.25050431 Predicted Change= -1.103373D-08 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00166 || 0.00180 [ YES ] 0.00166 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.586310 -1.989710 -0.470957 H 1.919422 -2.277531 -1.463049 C 0.231707 -2.055791 -0.141552 O -0.764628 -2.478930 -0.968729 C -0.425623 -2.852746 -2.296077 H 0.263397 -3.707144 -2.308977 H 0.024514 -2.015554 -2.845039 H -1.364973 -3.135857 -2.773337 C -0.184215 -1.611740 1.131320 O -1.544925 -1.484310 1.390985 C -2.109122 -0.360821 0.769068 C 0.749569 -1.233678 2.080926 H 0.399541 -0.921086 3.059891 C 2.105993 -1.179339 1.742754

H 2.826165 -0.828372 2.476280 C 2.528348 -1.496201 0.450730 C -3.321466 -0.573051 0.098082 O -3.886965 -1.809935 0.062018 H -3.231905 -2.419535 0.448796 C -3.925768 0.508105 -0.543396 H -4.866351 0.346856 -1.061218 C -3.299459 1.757389 -0.552638 H -3.771521 2.579243 -1.086162 C -2.075459 1.967555 0.094115 C -1.338474 3.289852 0.002563 H -2.007372 4.046201 -0.422903 C -0.061123 3.211355 -0.869142 H 0.239791 4.229028 -1.161641 H -0.261287 2.663967 -1.797291 C 1.155601 2.620563 -0.146591 C 2.020943 1.645888 -0.934633 H 2.117061 2.005105 -1.969502 H 1.419552 0.726370 -1.007893 C 3.397054 1.342842 -0.323225 H 3.285722 1.270191 0.763462 H 4.050918 2.205875 -0.498045 C 4.061292 0.062505 -0.890496 H 5.130510 0.242715 -1.058002 H 3.639795 -0.163546 -1.879565 C 3.945056 -1.197917 0.010131 H 4.369863 -2.052310 -0.533893 H 4.570324 -1.051341 0.899281 O 1.399004 2.915502 1.010595 H -1.041856 3.645009 0.996448 C -1.502190 0.887673 0.781019 H -0.565037 1.016686 1.311418 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.25050431 Predicted Change= -1.103373D-08 Zero-point correction (ZPE)= -1075.8664 0.38402 Internal Energy (U)= -1075.8451 0.40533 Enthalpy (H)= -1075.8442 0.40627 Gibbs Free Energy (G)= -1075.9161 0.33440 ------------------------------------------------------------------------------ Frequencies -- 27.6614 41.8558 57.9622

5.2.60 Intabd Supporting Information: 030-GS-C7-8-COout-Ph-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24810598 Predicted Change= -8.293531D-09 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00237 || 0.00180 [ NO ] 0.00237 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.663858 -1.913524 0.648233 H 2.214057 -1.870480 1.582044 C 0.272124 -2.021448 0.669152 O -0.491107 -2.099153 1.789528 C 0.136252 -1.860994 3.044047 H 0.624143 -0.878658 3.060180 H 0.870081 -2.641830 3.282756 H -0.665756 -1.885150 3.783576 C -0.426212 -1.953765 -0.553119 O -1.805702 -1.793799 -0.541875 C -2.241383 -0.484000 -0.335295 C 0.261322 -1.917245 -1.755908 H -0.309710 -1.877417 -2.678741 C 1.657274 -1.829025 -1.763386 H 2.185739 -1.738153 -2.708703 C 2.361743 -1.750141 -0.559566 C -3.620924 -0.292249 -0.509375 O -4.433712 -1.337050 -0.842518


S60

S60

H -3.870209 -2.128386 -0.897611 C -4.144818 0.987915 -0.348009 H -5.210896 1.133100 -0.493908 C -3.306740 2.057271 -0.015951 H -3.737123 3.048959 0.101825 C -1.933459 1.870222 0.171732 C -1.026005 3.018521 0.580229 H -1.587489 3.954190 0.481674 C 0.291746 3.152994 -0.211327 H 0.586347 4.211902 -0.277738 H 0.166575 2.830569 -1.255186 C 1.503915 2.426434 0.370559 C 2.810967 2.538360 -0.418479 H 3.591286 2.887506 0.270044 H 2.703453 3.293765 -1.205271 C 3.237194 1.188149 -1.052857 H 3.942657 1.396865 -1.867537 H 2.358479 0.732443 -1.524784 C 3.876274 0.196251 -0.062204 H 3.375451 0.286956 0.907121 H 4.927244 0.473207 0.098442 C 3.802519 -1.286582 -0.517069 H 4.268287 -1.401976 -1.504211 H 4.387688 -1.896076 0.183605 O 1.447056 1.793367 1.412333 H -0.764982 2.920848 1.642369 C -1.413974 0.578724 0.005451 H -0.357631 0.405688 0.159149 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24810598 Predicted Change= -8.293531D-09 Zero-point correction (ZPE)= -1075.8638 0.38422 Internal Energy (U)= -1075.8426 0.40550 Enthalpy (H)= -1075.8416 0.40644 Gibbs Free Energy (G)= -1075.9135 0.33455 ------------------------------------------------------------------------------ Frequencies -- 21.5609 37.2009 58.8114

5.2.61 Intacb Supporting Information: 030-GS-C7-8-11-12in-COin-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.25050429 Predicted Change= -1.211479D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00221 || 0.00180 [ NO ] 0.00221 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.586183 -1.989830 0.470837 H -1.919437 -2.277673 1.462873 C -0.231525 -2.055836 0.141630 O 0.764715 -2.478839 0.968986 C 0.425272 -2.854125 2.295806 H -0.263849 -3.708455 2.307515 H -0.024933 -2.017516 2.845610 H 1.364451 -3.137865 2.773029 C 0.184560 -1.611700 -1.131164 O 1.545298 -1.484233 -1.390621 C 2.109350 -0.360600 -0.768858 C -0.749097 -1.233575 -2.080870 H -0.398935 -0.920919 -3.059767 C -2.105568 -1.179305 -1.742891 H -2.825649 -0.828296 -2.476486 C -2.528101 -1.496300 -0.450953 C 3.321928 -0.572552 -0.098205 O 3.887732 -1.809308 -0.062331 H 3.232747 -2.419048 -0.449013 C 3.926140 0.508734 0.543130 H 4.866890 0.347691 1.060715 C 3.299547 1.757877 0.552552

H 3.771556 2.579831 1.085970 C 2.075336 1.967761 -0.093881 C 1.338051 3.289875 -0.002202 H 2.006773 4.046332 0.423346 C 0.060688 3.211053 0.869470 H -0.240244 4.228628 1.162276 H 0.260869 2.663366 1.797437 C -1.156061 2.620476 0.146763 C -2.021408 1.645603 0.934593 H -2.117611 2.004794 1.969481 H -1.420061 0.726083 1.007901 C -3.397524 1.342740 0.323109 H -3.286312 1.270510 -0.763622 H -4.051385 2.205704 0.498310 C -4.061731 0.062238 0.889966 H -5.131076 0.242214 1.056916 H -3.640693 -0.163689 1.879264 C -3.944916 -1.198166 -0.010622 H -4.369703 -2.052628 0.533316 H -4.570007 -1.051722 -0.899919 O -1.399607 2.915918 -1.010258 H 1.041367 3.645080 -0.996055 C 1.502132 0.887748 -0.780632 H 0.564811 1.016564 -1.310779 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.25050429 Predicted Change= -1.211479D-08 Zero-point correction (ZPE)= -1075.8664 0.38402 Internal Energy (U)= -1075.8451 0.40533 Enthalpy (H)= -1075.8442 0.40627 Gibbs Free Energy (G)= -1075.9161 0.33440 ------------------------------------------------------------------------------ Frequencies -- 27.6595 41.8448 57.9413

5.2.62 Intacd Supporting Information: 030-GS-C7-8-11-12in-Ph-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24014436 Predicted Change= -2.220791D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00188 || 0.00180 [ NO ] 0.00188 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.789717 -2.025054 0.296549 H 2.415894 -2.324755 1.130393 C 0.413794 -2.294435 0.326481 O -0.239173 -2.923066 1.342095 C 0.524849 -3.396220 2.440127 H 1.024843 -2.574301 2.969951 H 1.276765 -4.130168 2.122112 H -0.188210 -3.876718 3.112135 C -0.386142 -1.805516 -0.721162 O -1.773041 -1.779846 -0.571880 C -2.243843 -0.524060 -0.183755 C 0.195983 -1.190251 -1.821693 H -0.450579 -0.829007 -2.615768 C 1.566197 -0.943508 -1.847951 H 1.994600 -0.403947 -2.686816 C 2.364368 -1.291675 -0.752995 C -3.561332 -0.214859 -0.551297 O -4.332500 -1.122466 -1.215297 H -3.779318 -1.909502 -1.364208 C -4.064376 1.047931 -0.236739 H -5.082808 1.285037 -0.528843 C -3.261330 1.990663 0.413301 H -3.668869 2.976160 0.625786 C -1.948275 1.683801 0.787653 C -1.025095 2.686292 1.453689 H -1.622858 3.500180 1.880929 C 0.022615 3.336786 0.509662


S61

S61

H 0.515009 4.148369 1.069561 H -0.478770 3.791870 -0.349765 C 1.160720 2.476630 -0.056152 C 2.010706 1.652425 0.912830 H 1.561307 0.653873 0.974536 H 1.917361 2.081442 1.919529 C 3.512305 1.530315 0.562584 H 4.012855 1.090999 1.437564 H 3.917317 2.546556 0.466760 C 3.941168 0.745752 -0.696286 H 5.007909 0.959645 -0.849527 H 3.415438 1.152189 -1.563905 C 3.795177 -0.797485 -0.668088 H 4.368850 -1.195624 -1.516747 H 4.272814 -1.196601 0.236828 O 1.408642 2.511344 -1.249063 H -0.509969 2.213094 2.300432 C -1.468292 0.403146 0.498217 H -0.464487 0.129404 0.792372 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24014436 Predicted Change= -2.220791D-08 Zero-point correction (ZPE)= -1075.8560 0.38408 Internal Energy (U)= -1075.8347 0.40537 Enthalpy (H)= -1075.8338 0.40632 Gibbs Free Energy (G)= -1075.9059 0.33415 ------------------------------------------------------------------------------ Frequencies -- 19.1324 37.8483 56.4900

5.2.63 Intadb Supporting Information: 030-GS2-C7-8-Ph-COin-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24235401 Predicted Change= -6.814303D-09 ============================================================================== Optimization completed on the basis of negligible forces. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00435 || 0.00180 [ NO ] 0.00435 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.433871 -2.109544 -0.433393 H -1.787937 -2.317333 -1.437970 C -0.070386 -2.178058 -0.147084 O 0.908577 -2.510563 -1.033866 C 0.549233 -2.730335 -2.391748 H 0.068440 -1.844025 -2.823895 H -0.118280 -3.595415 -2.493783 H 1.485267 -2.927730 -2.915931 C 0.378292 -1.810411 1.138587 O 1.741297 -1.593566 1.337201 C 2.119379 -0.347905 0.800433 C -0.534810 -1.536220 2.143766 H -0.161719 -1.295534 3.134789 C -1.900551 -1.468333 1.845882 H -2.605074 -1.182787 2.622285 C -2.351820 -1.679470 0.542071 C 3.143873 -0.344359 -0.155004 O 3.766479 -1.496400 -0.520086 H 3.238178 -2.223371 -0.141844 C 3.491450 0.871661 -0.749294 H 4.280369 0.876898 -1.495190 C 2.787146 2.036724 -0.437772 H 3.041676 2.960408 -0.951631 C 1.746532 2.033622 0.500815 C 0.931703 3.278741 0.809113 H 1.208996 3.677963 1.794877 C -0.605924 3.065877 0.802687 H -1.078332 3.999264 1.132926 H -0.893668 2.284072 1.513457 C -1.146065 2.760738 -0.598014 C -1.763119 1.393642 -0.876536

H -1.104168 0.620242 -0.469016 H -1.791886 1.282479 -1.966181 C -3.196610 1.212939 -0.316730 H -3.800640 2.062543 -0.658718 H -3.186321 1.262484 0.780459 C -3.888457 -0.095615 -0.781638 H -3.510626 -0.360114 -1.778098 H -4.960411 0.099812 -0.913528 C -3.771760 -1.329869 0.153086 H -4.352258 -1.139395 1.064239 H -4.256409 -2.177803 -0.350364 O -1.062434 3.603870 -1.473826 H 1.164766 4.059692 0.077420 C 1.453510 0.822756 1.137960 H 0.662233 0.771443 1.877197 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24235401 Predicted Change= -6.814303D-09 Zero-point correction (ZPE)= -1075.8581 0.38420 Internal Energy (U)= -1075.8367 0.40559 Enthalpy (H)= -1075.8358 0.40654 Gibbs Free Energy (G)= -1075.9084 0.33390 ------------------------------------------------------------------------------ Frequencies -- 25.0449 38.6118 47.1206

5.2.64 Intadc Supporting Information: 030-GS-C7-8-Ph-C11-12in-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24014439 Predicted Change= -6.681857D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00103 || 0.00180 [ YES ] 0.00103 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.789482 -2.025251 0.296772 H 2.415506 -2.324954 1.130729 C 0.413542 -2.294530 0.326496 O -0.239667 -2.922984 1.342059 C 0.524130 -3.396241 2.440207 H 1.024200 -2.574399 2.970072 H 1.275956 -4.130331 2.122308 H -0.189100 -3.876586 3.112139 C -0.386198 -1.805545 -0.721276 O -1.773120 -1.779633 -0.572206 C -2.243815 -0.523809 -0.184025 C 0.196144 -1.190464 -1.821782 H -0.450251 -0.829197 -2.615985 C 1.566395 -0.943859 -1.847850 H 1.994961 -0.404389 -2.686690 C 2.364345 -1.291948 -0.752724 C -3.561389 -0.214650 -0.551249 O -4.332658 -1.122181 -1.215244 H -3.779713 -1.909452 -1.363803 C -4.064443 1.048103 -0.236480 H -5.082964 1.285145 -0.528323 C -3.261315 1.990823 0.413444 H -3.668843 2.976279 0.626151 C -1.948154 1.683991 0.787524 C -1.024934 2.686468 1.453501 H -1.622659 3.500414 1.880686 C 0.022849 3.336839 0.509438 H 0.515236 4.148476 1.069263 H -0.478494 3.791851 -0.350053 C 1.160977 2.476621 -0.056228 C 2.011007 1.652568 0.912852 H 1.561525 0.654071 0.974863 H 1.917800 2.081829 1.919460 C 3.512568 1.530264 0.562518 H 4.013151 1.091132 1.437570


S62

S62

H 3.917637 2.546451 0.466427 C 3.941329 0.745351 -0.696186 H 5.008089 0.959109 -0.849459 H 3.415655 1.151665 -1.563891 C 3.795185 -0.797848 -0.667625 H 4.368996 -1.196290 -1.516042 H 4.272591 -1.196792 0.237499 O 1.408909 2.511203 -1.249141 H -0.509816 2.213338 2.300293 C -1.468179 0.403407 0.497864 H -0.464343 0.129667 0.791874 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24014439 Predicted Change= -6.681857D-09 Zero-point correction (ZPE)= -1075.8560 0.38407 Internal Energy (U)= -1075.8347 0.40537 Enthalpy (H)= -1075.8338 0.40632 Gibbs Free Energy (G)= -1075.9059 0.33415 ------------------------------------------------------------------------------ Frequencies -- 19.1131 37.8466 56.4945

5.2.65 Intbac Supporting Information: 030-GS2-COin-C7-8out-11-12out-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.25050429 Predicted Change= -1.209637D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00237 || 0.00180 [ NO ] 0.00237 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.586151 -1.989970 -0.470829 H 1.919226 -2.277995 -1.462876 C 0.231562 -2.055968 -0.141354 O -0.764805 -2.479241 -0.968421 C -0.425813 -2.853256 -2.295713 H 0.263190 -3.707672 -2.308485 H 0.024339 -2.016156 -2.844804 H -1.365174 -3.136418 -2.772923 C -0.184308 -1.611653 1.131445 O -1.545014 -1.484153 1.391101 C -2.109125 -0.360659 0.769106 C 0.749510 -1.233415 2.080942 H 0.399523 -0.920635 3.059862 C 2.105918 -1.179164 1.742709 H 2.826122 -0.828047 2.476132 C 2.528223 -1.496293 0.450737 C -3.321382 -0.572894 0.097976 O -3.886872 -1.809781 0.061841 H -3.231872 -2.419364 0.448748 C -3.925600 0.508260 -0.543593 H -4.866118 0.347012 -1.061532 C -3.299270 1.757531 -0.552783 H -3.771253 2.579382 -1.086384 C -2.075343 1.967695 0.094117 C -1.338321 3.289970 0.002578 H -2.007207 4.046355 -0.422838 C -0.061012 3.211443 -0.869183 H 0.239930 4.229107 -1.161678 H -0.261231 2.664062 -1.797327 C 1.155719 2.620612 -0.146687 C 2.020946 1.645778 -0.934694 H 2.116960 2.004857 -1.969616 H 1.419512 0.726273 -1.007754 C 3.397113 1.342739 -0.323393 H 3.285896 1.270212 0.763314 H 4.051026 2.205704 -0.498366 C 4.061202 0.062305 -0.890614 H 5.130425 0.242416 -1.058187

H 3.639619 -0.163720 -1.879657 C 3.944918 -1.198084 0.010034 H 4.369626 -2.052517 -0.534001 H 4.570229 -1.051549 0.899162 O 1.399242 2.915674 1.010447 H -1.041628 3.645073 0.996456 C -1.502171 0.887825 0.781105 H -0.565052 1.016827 1.311564 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.25050429 Predicted Change= -1.209637D-08 Zero-point correction (ZPE)= -1075.8664 0.38402 Internal Energy (U)= -1075.8451 0.40533 Enthalpy (H)= -1075.8442 0.40627 Gibbs Free Energy (G)= -1075.9161 0.33440 ------------------------------------------------------------------------------ Frequencies -- 27.6640 41.8530 57.9635

5.2.66 Intbad Supporting Information: 030-GS-COin-C7-8out-Ph-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24810597 Predicted Change= -4.102935D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00106 || 0.00180 [ YES ] 0.00106 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.663750 -1.913556 0.648048 H 2.213899 -1.870584 1.581890 C 0.272017 -2.021484 0.668859 O -0.491320 -2.099271 1.789141 C 0.136195 -1.862710 3.043856 H 0.624256 -0.880474 3.061121 H 0.869930 -2.643946 3.281546 H -0.665735 -1.887606 3.783441 C -0.426235 -1.953622 -0.553465 O -1.805716 -1.793621 -0.542264 C -2.241386 -0.483821 -0.335484 C 0.261371 -1.916956 -1.756197 H -0.309601 -1.877006 -2.679060 C 1.657337 -1.828788 -1.763579 H 2.185864 -1.737815 -2.708844 C 2.361714 -1.750047 -0.559703 C -3.620936 -0.292080 -0.509287 O -4.433793 -1.336803 -0.842502 H -3.870379 -2.128218 -0.897419 C -4.144831 0.988067 -0.347625 H -5.210950 1.133225 -0.493298 C -3.306721 2.057371 -0.015590 H -3.737065 3.049051 0.102420 C -1.933377 1.870321 0.171797 C -1.025946 3.018636 0.580282 H -1.587406 3.954307 0.481580 C 0.291900 3.153078 -0.211122 H 0.586542 4.211987 -0.277405 H 0.166815 2.830752 -1.255018 C 1.503989 2.426462 0.370842 C 2.811129 2.538443 -0.418061 H 3.591428 2.887350 0.270596 H 2.703742 3.294013 -1.204711 C 3.237233 1.188271 -1.052612 H 3.942717 1.396982 -1.867281 H 2.358487 0.732660 -1.524566 C 3.876224 0.196264 -0.062015 H 3.375320 0.286882 0.907275 H 4.927186 0.473203 0.098738 C 3.802494 -1.286513 -0.517051 H 4.268315 -1.401777 -1.504177 H 4.387619 -1.896098 0.183584


S63

S63

O 1.447031 1.793315 1.412557 H -0.765052 2.921083 1.642470 C -1.413919 0.578873 0.005259 H -0.357547 0.405809 0.158753 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24810597 Predicted Change= -4.102935D-09 Zero-point correction (ZPE)= -1075.8638 0.38422 Internal Energy (U)= -1075.8426 0.40550 Enthalpy (H)= -1075.8416 0.40644 Gibbs Free Energy (G)= -1075.9135 0.33456 ------------------------------------------------------------------------------ Frequencies -- 21.5563 37.2256 58.8143

5.2.67 Intbca Supporting Information: 030-GS-COout-C11-12out-7-8-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.25050427 Predicted Change= -2.195042D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00211 || 0.00180 [ NO ] 0.00211 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.586043 -1.989809 -0.470921 H 1.919116 -2.277704 -1.463008 C 0.231431 -2.055787 -0.141496 O -0.764930 -2.478870 -0.968652 C -0.425994 -2.852417 -2.296102 H 0.262910 -3.706912 -2.309205 H 0.024250 -2.015156 -2.844861 H -1.365393 -3.135287 -2.773399 C -0.184421 -1.611712 1.131384 O -1.545142 -1.484204 1.391049 C -2.109217 -0.360683 0.769175 C 0.749401 -1.233700 2.080981 H 0.399399 -0.921102 3.059954 C 2.105805 -1.179457 1.742774 H 2.826033 -0.828565 2.476288 C 2.528129 -1.496383 0.450744 C -3.321482 -0.572791 0.097979 O -3.887033 -1.809657 0.061739 H -3.232072 -2.419294 0.448628 C -3.925634 0.508415 -0.543522 H -4.866143 0.347227 -1.061503 C -3.299239 1.757664 -0.552637 H -3.771163 2.579562 -1.086219 C -2.075330 1.967725 0.094289 C -1.338118 3.289889 0.002740 H -2.006900 4.046401 -0.422611 C -0.060887 3.211086 -0.869139 H 0.240068 4.228616 -1.162083 H -0.261194 2.663352 -1.797050 C 1.155946 2.620427 -0.146605 C 2.021238 1.645777 -0.934750 H 2.117445 2.005318 -1.969512 H 1.419834 0.726307 -1.008374 C 3.397307 1.342537 -0.323336 H 3.285965 1.269951 0.763352 H 4.051341 2.205450 -0.498146 C 4.061291 0.062056 -0.890562 H 5.130521 0.242028 -1.058192 H 3.639649 -0.164007 -1.879566 C 3.944884 -1.198275 0.010173 H 4.369599 -2.052756 -0.533786 H 4.570131 -1.051703 0.899335 O 1.399540 2.915553 1.010483 H -1.041266 3.644918 0.996592 C -1.502231 0.887779 0.781273 H -0.565132 1.016739 1.311763

------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.25050427 Predicted Change= -2.195042D-08 Zero-point correction (ZPE)= -1075.8664 0.38402 Internal Energy (U)= -1075.8451 0.40533 Enthalpy (H)= -1075.8442 0.40627 Gibbs Free Energy (G)= -1075.9161 0.33440 ------------------------------------------------------------------------------ Frequencies -- 27.6688 41.8550 57.9383

5.2.68 Intbcd Supporting Information: 030-GS-COout-C11-12out-Ph-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24756486 Predicted Change= -3.001666D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00069 || 0.00180 [ YES ] 0.00069 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.689714 -1.537996 0.793766 H 2.055594 -1.305011 1.787257 C 0.329615 -1.786741 0.597624 O -0.617612 -1.776722 1.570074 C -0.259507 -1.266991 2.854083 H 0.147164 -0.252940 2.773034 H 0.463996 -1.923773 3.354153 H -1.186304 -1.250000 3.429540 C -0.136050 -2.002469 -0.714969 O -1.510345 -1.994989 -0.953768 C -2.063061 -0.723406 -0.759835 C 0.756944 -2.091792 -1.773126 H 0.365327 -2.279757 -2.768524 C 2.118767 -1.852363 -1.560670 H 2.804632 -1.869943 -2.403844 C 2.584221 -1.506947 -0.287599 C -3.296199 -0.665029 -0.099267 O -3.925154 -1.802565 0.302020 H -3.296216 -2.532172 0.154586 C -3.859605 0.587858 0.153866 H -4.817320 0.631272 0.663410 C -3.173390 1.754061 -0.193069 H -3.612219 2.718280 0.053212 C -1.928541 1.698799 -0.833136 C -1.095174 2.932236 -1.115253 H -0.454246 2.753178 -1.987514 C -0.219348 3.385353 0.087091 H -0.860830 3.653558 0.932005 H 0.334358 4.287612 -0.215030 C 0.802392 2.379778 0.621065 C 1.879768 1.841580 -0.323478 H 2.047013 2.545340 -1.149431 H 1.457394 0.936852 -0.778731 C 3.205011 1.489624 0.380549 H 2.969285 1.059280 1.359186 H 3.742809 2.423847 0.586135 C 4.128944 0.537504 -0.416837 H 5.174730 0.809651 -0.224525 H 3.973093 0.683846 -1.494483 C 3.986160 -0.973685 -0.085346 H 4.696284 -1.529444 -0.711154 H 4.294139 -1.132327 0.956047 O 0.759882 2.025527 1.787708 H -1.742550 3.777990 -1.377705 C -1.408568 0.438600 -1.145022 H -0.462847 0.356815 -1.668504 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm


S64

S64

============================================================================== SCF Energy= -1076.24756486 Predicted Change= -3.001666D-09 Zero-point correction (ZPE)= -1075.8632 0.38436 Internal Energy (U)= -1075.8420 0.40553 Enthalpy (H)= -1075.8410 0.40647 Gibbs Free Energy (G)= -1075.9120 0.33551 ------------------------------------------------------------------------------ Frequencies -- 37.4554 55.5841 59.9463

5.2.69 Intbda Supporting Information: 030-GS-COin-Ph-C7-8-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24810486 Predicted Change= -1.477724D-07 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00004 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.01791 || 0.00180 [ NO ] 0.01791 || 0.00180 [ NO ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.665290 -1.913793 0.646083 H 2.216735 -1.871781 1.579196 C 0.273614 -2.022471 0.668616 O -0.488198 -2.102127 1.789832 C 0.141089 -1.867692 3.044032 H 0.629119 -0.885465 3.062422 H 0.875271 -2.649244 3.279298 H -0.659765 -1.893957 3.784746 C -0.426316 -1.953458 -0.552656 O -1.805879 -1.794204 -0.539240 C -2.241623 -0.484293 -0.333395 C 0.259664 -1.914797 -1.756271 H -0.312591 -1.874025 -2.678321 C 1.655582 -1.825958 -1.765418 H 2.182848 -1.733627 -2.711278 C 2.361557 -1.748500 -0.562386 C -3.620741 -0.292072 -0.510430 O -4.433090 -1.336550 -0.845631 H -3.869583 -2.127917 -0.900261 C -4.144594 0.988193 -0.349774 H -5.210312 1.133786 -0.497897 C -3.306827 2.057200 -0.015814 H -3.737112 3.049037 0.101118 C -1.934020 1.869655 0.174705 C -1.026787 3.017575 0.584472 H -1.588617 3.953206 0.487658 C 0.290199 3.153477 -0.208102 H 0.584255 4.212581 -0.273576 H 0.164271 2.832066 -1.252223 C 1.503054 2.426718 0.372048 C 2.809396 2.539781 -0.418016 H 3.590340 2.888283 0.270121 H 2.701033 3.295940 -1.203973 C 3.235144 1.190223 -1.054116 H 3.939344 1.399781 -1.869660 H 2.355866 0.734569 -1.525056 C 3.875913 0.197874 -0.065093 H 3.376128 0.287545 0.904853 H 4.926955 0.475223 0.094520 C 3.802231 -1.284553 -0.521102 H 4.266932 -1.398976 -1.508856 H 4.388355 -1.894432 0.178435 O 1.447263 1.792594 1.413238 H -0.764838 2.918442 1.646257 C -1.414617 0.577982 0.009514 H -0.358641 0.404707 0.165497 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24810486 Predicted Change= -1.477724D-07 Zero-point correction (ZPE)= -1075.8638 0.38422

Internal Energy (U)= -1075.8426 0.40550 Enthalpy (H)= -1075.8416 0.40644 Gibbs Free Energy (G)= -1075.9135 0.33454 ------------------------------------------------------------------------------ Frequencies -- 21.3170 37.1429 58.7328

5.2.70 Intbdc Supporting Information: 030-GS-COout-Ph-C11-12in-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24756462 Predicted Change= -4.489259D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00280 || 0.00180 [ NO ] 0.00280 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.689445 -1.538625 0.793790 H 2.055033 -1.306140 1.787512 C 0.329419 -1.787329 0.597135 O -0.618026 -1.778130 1.569404 C -0.260638 -1.267988 2.853458 H 0.146128 -0.253995 2.772333 H 0.462527 -1.924672 3.354164 H -1.187768 -1.250768 3.428382 C -0.135930 -2.002276 -0.715682 O -1.510175 -1.994682 -0.954832 C -2.062834 -0.723131 -0.760274 C 0.757339 -2.090926 -1.773670 H 0.366013 -2.278314 -2.769291 C 2.119087 -1.851558 -1.560726 H 2.805139 -1.868546 -2.403764 C 2.584211 -1.506863 -0.287336 C -3.295747 -0.664975 -0.099274 O -3.924564 -1.802623 0.301849 H -3.295547 -2.532137 0.154296 C -3.859075 0.587838 0.154435 H -4.816607 0.631071 0.664341 C -3.173000 1.754144 -0.192396 H -3.611749 2.718287 0.054319 C -1.928359 1.699100 -0.832900 C -1.095136 2.932657 -1.114966 H -0.454218 2.753658 -1.987242 C -0.219217 3.385803 0.087315 H -0.860605 3.654153 0.932240 H 0.334677 4.287893 -0.214945 C 0.802169 2.379831 0.621218 C 1.879680 1.841580 -0.323104 H 2.047080 2.545212 -1.149128 H 1.457364 0.936768 -0.778236 C 3.204851 1.489665 0.381112 H 2.969002 1.059200 1.359667 H 3.742584 2.423894 0.586801 C 4.128922 0.537570 -0.416203 H 5.174675 0.809773 -0.223769 H 3.973194 0.683853 -1.493865 C 3.986075 -0.973564 -0.084540 H 4.696450 -1.529453 -0.709948 H 4.293610 -1.132028 0.957007 O 0.759199 2.025049 1.787680 H -1.742585 3.778363 -1.377398 C -1.408437 0.438986 -1.145275 H -0.462819 0.357380 -1.668992 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24756462 Predicted Change= -4.489259D-08 Zero-point correction (ZPE)= -1075.8632 0.38436 Internal Energy (U)= -1075.8420 0.40553 Enthalpy (H)= -1075.8410 0.40647 Gibbs Free Energy (G)= -1075.9120 0.33550 ------------------------------------------------------------------------------


S65

S65

Frequencies -- 37.4686 55.5439 59.9353

5.2.71 Intcab Supporting Information: 030-GS-C11-12in-7-8-COin-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.25050429 Predicted Change= -1.151038D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00225 || 0.00180 [ NO ] 0.00225 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.586177 -1.989843 0.470832 H -1.919428 -2.277691 1.462868 C -0.231520 -2.055846 0.141618 O 0.764724 -2.478859 0.968962 C 0.425293 -2.854151 2.295786 H -0.263827 -3.708481 2.307498 H -0.024907 -2.017543 2.845594 H 1.364477 -3.137891 2.772998 C 0.184556 -1.611699 -1.131174 O 1.545293 -1.484225 -1.390637 C 2.109341 -0.360597 -0.768864 C -0.749106 -1.233570 -2.080874 H -0.398948 -0.920908 -3.059771 C -2.105574 -1.179305 -1.742888 H -2.825662 -0.828294 -2.476477 C -2.528100 -1.496308 -0.450950 C 3.321912 -0.572552 -0.098197 O 3.887711 -1.809309 -0.062316 H 3.232727 -2.419046 -0.449005 C 3.926121 0.508732 0.543146 H 4.866864 0.347687 1.060740 C 3.299529 1.757876 0.552560 H 3.771534 2.579828 1.085984 C 2.075327 1.967764 -0.093887 C 1.338050 3.289882 -0.002217 H 2.006780 4.046340 0.423316 C 0.060693 3.211082 0.869466 H -0.240230 4.228664 1.162251 H 0.260878 2.663411 1.797442 C -1.156062 2.620498 0.146773 C -2.021385 1.645600 0.934597 H -2.117586 2.004774 1.969491 H -1.420025 0.726087 1.007887 C -3.397503 1.342730 0.323121 H -3.286296 1.270492 -0.763611 H -4.051365 2.205694 0.498317 C -4.061704 0.062230 0.889989 H -5.131045 0.242211 1.056962 H -3.640647 -0.163704 1.879277 C -3.944911 -1.198172 -0.010604 H -4.369696 -2.052633 0.533334 H -4.570009 -1.051721 -0.899894 O -1.399625 2.915950 -1.010243 H 1.041360 3.645078 -0.996071 C 1.502125 0.887753 -0.780645 H 0.564810 1.016572 -1.310800 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.25050429 Predicted Change= -1.151038D-08 Zero-point correction (ZPE)= -1075.8664 0.38402 Internal Energy (U)= -1075.8451 0.40533 Enthalpy (H)= -1075.8442 0.40627 Gibbs Free Energy (G)= -1075.9161 0.33440 ------------------------------------------------------------------------------ Frequencies -- 27.6604 41.8466 57.9393

5.2.72 Intcad Supporting Information: 030-GS-C11-12in-7-8-Ph-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24014435 Predicted Change= -2.173100D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00203 || 0.00180 [ NO ] 0.00203 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.789567 2.025226 0.296543 H -2.415676 2.324984 1.130417 C -0.413621 2.294537 0.326411 O 0.239411 2.923155 1.341985 C -0.524561 3.396591 2.439929 H -1.024603 2.574833 2.969945 H -1.276436 4.130511 2.121752 H 0.188528 3.877194 3.111827 C 0.386243 1.805515 -0.721227 O 1.773163 1.779772 -0.571919 C 2.243918 0.523992 -0.183691 C -0.195950 1.190150 -1.821679 H 0.450566 0.828802 -2.615760 C -1.566175 0.943488 -1.847870 H -1.994639 0.403865 -2.686661 C -2.364293 1.291817 -0.752924 C 3.561343 0.214657 -0.551334 O 4.332523 1.122175 -1.215434 H 3.779393 1.909264 -1.364285 C 4.064299 -1.048168 -0.236773 H 5.082679 -1.285406 -0.528951 C 3.261215 -1.990798 0.413368 H 3.668675 -2.976338 0.625813 C 1.948206 -1.683829 0.787802 C 1.024970 -2.686301 1.453763 H 1.622682 -3.500245 1.880991 C -0.022697 -3.336728 0.509681 H -0.515070 -4.148390 1.069493 H 0.478706 -3.791744 -0.349772 C -1.160909 -2.476683 -0.056104 C -2.010964 -1.652555 0.912875 H -1.561474 -0.654070 0.974837 H -1.917777 -2.081758 1.919509 C -3.512518 -1.530284 0.562449 H -4.013171 -1.091052 1.437414 H -3.917579 -2.546484 0.466447 C -3.941203 -0.745509 -0.696370 H -5.007945 -0.959312 -0.849733 H -3.415453 -1.151879 -1.563999 C -3.795115 0.797700 -0.667898 H -4.368832 1.196052 -1.516419 H -4.272635 1.196707 0.237139 O -1.408854 -2.511511 -1.249009 H 0.509833 -2.213115 2.300508 C 1.468335 -0.403125 0.498381 H 0.464556 -0.129301 0.792519 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24014435 Predicted Change= -2.173100D-08 Zero-point correction (ZPE)= -1075.8560 0.38407 Internal Energy (U)= -1075.8347 0.40537 Enthalpy (H)= -1075.8338 0.40632 Gibbs Free Energy (G)= -1075.9059 0.33415 ------------------------------------------------------------------------------ Frequencies -- 19.1094 37.8468 56.4826

5.2.73 Intcba Supporting Information: 030-GS-C11-12in-Coin-C7-8-Galeon.log


S66

S66

------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.25050427 Predicted Change= -1.904368D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00217 || 0.00180 [ NO ] 0.00217 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.586019 -1.989799 -0.470925 H 1.919093 -2.277683 -1.463013 C 0.231419 -2.055774 -0.141493 O -0.764953 -2.478833 -0.968658 C -0.426018 -2.852461 -2.296068 H 0.262902 -3.706941 -2.309134 H 0.024218 -2.015233 -2.844898 H -1.365412 -3.135374 -2.773363 C -0.184441 -1.611714 1.131397 O -1.545155 -1.484204 1.391062 C -2.109224 -0.360668 0.769177 C 0.749386 -1.233725 2.080991 H 0.399399 -0.921128 3.059971 C 2.105798 -1.179485 1.742780 H 2.826021 -0.828602 2.476301 C 2.528115 -1.496390 0.450748 C -3.321476 -0.572773 0.097966 O -3.887030 -1.809635 0.061712 H -3.232090 -2.419278 0.448612 C -3.925620 0.508440 -0.543544 H -4.866124 0.347251 -1.061532 C -3.299210 1.757681 -0.552647 H -3.771123 2.579587 -1.086232 C -2.075309 1.967734 0.094300 C -1.338093 3.289896 0.002757 H -2.006872 4.046417 -0.422582 C -0.060863 3.211108 -0.869125 H 0.240088 4.228646 -1.162042 H -0.261178 2.663390 -1.797049 C 1.155967 2.620432 -0.146607 C 2.021241 1.645767 -0.934753 H 2.117442 2.005293 -1.969523 H 1.419822 0.726304 -1.008356 C 3.397317 1.342518 -0.323357 H 3.285986 1.269943 0.763334 H 4.051356 2.205422 -0.498188 C 4.061277 0.062025 -0.890583 H 5.130509 0.241985 -1.058226 H 3.639623 -0.164037 -1.879582 C 3.944867 -1.198293 0.010166 H 4.369572 -2.052789 -0.533778 H 4.570124 -1.051714 0.899320 O 1.399574 2.915554 1.010481 H -1.041241 3.644910 0.996616 C -1.502231 0.887788 0.781281 H -0.565129 1.016735 1.311790 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.25050427 Predicted Change= -1.904368D-08 Zero-point correction (ZPE)= -1075.8664 0.38402 Internal Energy (U)= -1075.8451 0.40533 Enthalpy (H)= -1075.8442 0.40627 Gibbs Free Energy (G)= -1075.9161 0.33440 ------------------------------------------------------------------------------ Frequencies -- 27.6709 41.8501 57.9388

5.2.74 Intcbd Supporting Information: 030-GS-C11-12in-Coin-Ph-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ==============================================================================

# b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24756486 Predicted Change= -2.808180D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00058 || 0.00180 [ YES ] 0.00058 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.689703 -1.538001 0.793769 H 2.055587 -1.304996 1.787254 C 0.329603 -1.786742 0.597635 O -0.617622 -1.776698 1.570085 C -0.259499 -1.266992 2.854099 H 0.147158 -0.252933 2.773068 H 0.464022 -1.923776 3.354137 H -1.186285 -1.250032 3.429576 C -0.136068 -2.002485 -0.714955 O -1.510360 -1.995001 -0.953750 C -2.063068 -0.723399 -0.759821 C 0.756924 -2.091827 -1.773111 H 0.365304 -2.279799 -2.768506 C 2.118750 -1.852405 -1.560663 H 2.804614 -1.869989 -2.403840 C 2.584208 -1.506970 -0.287599 C -3.296207 -0.665017 -0.099262 O -3.925164 -1.802545 0.302019 H -3.296251 -2.532160 0.154588 C -3.859611 0.587875 0.153858 H -4.817334 0.631296 0.663387 C -3.173385 1.754069 -0.193078 H -3.612208 2.718295 0.053185 C -1.928528 1.698798 -0.833139 C -1.095165 2.932234 -1.115262 H -0.454248 2.753180 -1.987528 C -0.219336 3.385359 0.087077 H -0.860815 3.653563 0.931987 H 0.334353 4.287626 -0.215057 C 0.802420 2.379804 0.621057 C 1.879773 1.841569 -0.323487 H 2.047014 2.545292 -1.149474 H 1.457378 0.936833 -0.778708 C 3.205025 1.489620 0.380526 H 2.969316 1.059298 1.359172 H 3.742827 2.423845 0.586080 C 4.128939 0.537482 -0.416857 H 5.174729 0.809619 -0.224544 H 3.973091 0.683821 -1.494498 C 3.986146 -0.973704 -0.085354 H 4.696266 -1.529467 -0.711157 H 4.294128 -1.132346 0.956039 O 0.759938 2.025600 1.787712 H -1.742545 3.777987 -1.377712 C -1.408558 0.438598 -1.145014 H -0.462838 0.356801 -1.668500 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24756486 Predicted Change= -2.808180D-09 Zero-point correction (ZPE)= -1075.8632 0.38436 Internal Energy (U)= -1075.8420 0.40553 Enthalpy (H)= -1075.8410 0.40647 Gibbs Free Energy (G)= -1075.9120 0.33550 ------------------------------------------------------------------------------ Frequencies -- 37.4501 55.5731 59.9384

5.2.75 Intcda Supporting Information: 030-GS-C11-12out-Ph-C7-8-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------


S67

S67

Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23998124 Predicted Change= -1.613192D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00076 || 0.00180 [ YES ] 0.00076 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.341584 -2.104289 0.567040 H 1.709214 -2.356522 1.556280 C -0.032126 -2.132626 0.304306 O -0.997593 -2.460897 1.205086 C -0.598516 -2.802698 2.523565 H -0.080746 -1.969217 3.016282 H 0.051349 -3.687415 2.531111 H -1.519878 -3.025708 3.064003 C -0.484970 -1.710240 -0.960362 O -1.836018 -1.423913 -1.137163 C -2.207376 -0.198627 -0.579408 C 0.420136 -1.410675 -1.967570 H 0.035626 -1.093635 -2.932219 C 1.789945 -1.405527 -1.698700 H 2.485141 -1.103204 -2.476318 C 2.256171 -1.675462 -0.408120 C -3.582067 -0.013985 -0.375243 O -4.474955 -0.986633 -0.714998 H -3.956867 -1.754033 -1.015474 C -4.016969 1.185710 0.186494 H -5.082487 1.328972 0.338146 C -3.095221 2.166655 0.566371 H -3.459053 3.082831 1.025533 C -1.720671 1.980422 0.380202 C -0.704022 2.984650 0.898013 H -1.222532 3.930417 1.096586 C 0.498857 3.307446 -0.019530 H 0.998053 4.194663 0.403025 H 0.156971 3.590861 -1.019807 C 1.639265 2.296822 -0.221443 C 2.134299 1.476716 0.969262 H 1.481814 0.598220 1.056521 H 1.960450 2.055603 1.886943 C 3.620152 1.053349 0.929124 H 3.862791 0.631696 1.915364 H 4.220237 1.968693 0.840946 C 4.121446 0.078985 -0.160115 H 5.218968 0.103500 -0.115300 H 3.841810 0.468596 -1.142020 C 3.704331 -1.410224 -0.049468 H 4.356657 -1.983906 -0.722124 H 3.911157 -1.777362 0.964678 O 2.171497 2.219030 -1.315667 H -0.330387 2.649798 1.877385 C -1.299563 0.790721 -0.223190 H -0.249850 0.623714 -0.414975 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23998124 Predicted Change= -1.613192D-09 Zero-point correction (ZPE)= -1075.8559 0.38406 Internal Energy (U)= -1075.8345 0.40538 Enthalpy (H)= -1075.8336 0.40633 Gibbs Free Energy (G)= -1075.9061 0.33385 ------------------------------------------------------------------------------ Frequencies -- 13.0455 38.1546 53.9097

5.2.76 Intcdb Supporting Information: 030-GS2-C11-12out-Ph-COin-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24756472 Predicted Change= -2.587632D-08

============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00193 || 0.00180 [ NO ] 0.00193 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.689708 -1.538433 0.793658 H 2.055608 -1.305894 1.787252 C 0.329610 -1.787147 0.597438 O -0.617562 -1.777535 1.569938 C -0.259662 -1.267343 2.853850 H 0.146922 -0.253282 2.772530 H 0.463817 -1.923913 3.354218 H -1.186538 -1.250247 3.429182 C -0.136084 -2.002435 -0.715222 O -1.510403 -1.994904 -0.953944 C -2.063063 -0.723323 -0.759902 C 0.756894 -2.091307 -1.773432 H 0.365304 -2.278923 -2.768907 C 2.118704 -1.851888 -1.560906 H 2.804556 -1.869107 -2.404096 C 2.584181 -1.506940 -0.287705 C -3.296150 -0.664945 -0.099239 O -3.925162 -1.802490 0.301931 H -3.296245 -2.532116 0.154518 C -3.859471 0.587946 0.154073 H -4.817139 0.631320 0.663712 C -3.173229 1.754156 -0.192793 H -3.611960 2.718377 0.053643 C -1.928420 1.698882 -0.832937 C -1.095062 2.932286 -1.115184 H -0.454204 2.753108 -1.987466 C -0.219091 3.385721 0.086994 H -0.860526 3.654274 0.931820 H 0.334667 4.287791 -0.215528 C 0.802411 2.380027 0.621176 C 1.879923 1.841764 -0.323226 H 2.047544 2.545653 -1.148979 H 1.457528 0.937178 -0.778723 C 3.204899 1.489362 0.381054 H 2.968741 1.058528 1.359361 H 3.742731 2.423395 0.587339 C 4.128918 0.537462 -0.416578 H 5.174700 0.809657 -0.224311 H 3.972984 0.683931 -1.494187 C 3.986158 -0.973775 -0.085315 H 4.696278 -1.529477 -0.711158 H 4.294078 -1.132559 0.956078 O 0.759462 2.025535 1.787705 H -1.742473 3.777996 -1.377709 C -1.408544 0.438689 -1.144992 H -0.462832 0.356913 -1.668494 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24756472 Predicted Change= -2.587632D-08 Zero-point correction (ZPE)= -1075.8632 0.38436 Internal Energy (U)= -1075.8420 0.40553 Enthalpy (H)= -1075.8410 0.40647 Gibbs Free Energy (G)= -1075.9120 0.33550 ------------------------------------------------------------------------------ Frequencies -- 37.4337 55.5538 59.9234

5.2.77 Intdab Supporting Information: 030-GS3-Ph-C7-8in-COin-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24720198 Predicted Change= -4.476163D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass?


S68

S68

Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00150 || 0.00180 [ YES ] 0.00150 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.639362 -1.877396 0.532434 H 2.178214 -1.944362 1.471382 C 0.252612 -2.036783 0.516722 O -0.521000 -2.285144 1.604516 C 0.101647 -2.298520 2.882422 H 0.589567 -1.339633 3.097388 H 0.836945 -3.109686 2.962717 H -0.702203 -2.468215 3.600403 C -0.433874 -1.844165 -0.699231 O -1.818072 -1.722571 -0.683468 C -2.273977 -0.445905 -0.350852 C 0.267006 -1.629169 -1.875631 H -0.293712 -1.493955 -2.795798 C 1.659680 -1.495634 -1.849650 H 2.197494 -1.282193 -2.769754 C 2.346826 -1.543564 -0.634568 C -3.661395 -0.261560 -0.451886 O -4.477395 -1.288486 -0.829960 H -3.911428 -2.068432 -0.963524 C -4.190171 0.996493 -0.171205 H -5.263200 1.136825 -0.259837 C -3.350884 2.053309 0.199118 H -3.786672 3.029101 0.399998 C -1.969274 1.871941 0.313262 C -1.031769 2.996666 0.718027 H -1.583838 3.942737 0.692548 C 0.225766 3.126126 -0.168862 H 0.599387 4.161562 -0.122924 H -0.015797 2.943359 -1.222778 C 1.427174 2.266163 0.246928 C 2.395437 1.901227 -0.872667 H 2.453152 2.760881 -1.555861 H 1.904673 1.109748 -1.456187 C 3.821580 1.491311 -0.459282 H 4.227240 2.287723 0.178292 H 4.437200 1.492163 -1.370095 C 4.047889 0.154884 0.277916 H 3.448791 0.142949 1.193522 H 5.099401 0.150960 0.595268 C 3.806646 -1.153503 -0.522227 H 4.247366 -1.062694 -1.523689 H 4.357643 -1.958258 -0.016591 O 1.600583 1.926803 1.404876 H -0.692889 2.858600 1.753388 C -1.449180 0.601097 0.037370 H -0.386857 0.427907 0.135581 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24720198 Predicted Change= -4.476163D-09 Zero-point correction (ZPE)= -1075.8631 0.38408 Internal Energy (U)= -1075.8417 0.40541 Enthalpy (H)= -1075.8408 0.40635 Gibbs Free Energy (G)= -1075.9131 0.33400 ------------------------------------------------------------------------------ Frequencies -- 17.6463 32.2204 50.4839

5.2.78 Intdac Supporting Information: 030-GS-Ph-C7-8in-11-12in-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24014430 Predicted Change= -1.071027D-07 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00008 || 0.00045 [ YES ] 0.00001 || 0.00030 [ YES ] Displ 0.00138 || 0.00180 [ YES ] 0.00138 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms)

Type X Y Z ------------------------------------------------------------------------------ C 1.790050 -2.025341 0.296613 H 2.416073 -2.324876 1.130651 C 0.414106 -2.294887 0.326409 O -0.238901 -2.923302 1.342161 C 0.525073 -3.396413 2.440177 H 1.025207 -2.574549 2.969968 H 1.276945 -4.130494 2.122247 H -0.188007 -3.876803 3.112294 C -0.385778 -1.805936 -0.721249 O -1.772694 -1.779947 -0.572064 C -2.243582 -0.524118 -0.183877 C 0.196500 -1.190867 -1.821864 H -0.450074 -0.829780 -2.616019 C 1.566641 -0.944021 -1.847961 H 1.995129 -0.404427 -2.686750 C 2.364677 -1.291879 -0.752801 C -3.561231 -0.215326 -0.551069 O -4.332335 -1.123076 -1.214972 H -3.779318 -1.910222 -1.363578 C -4.064622 1.047374 -0.236429 H -5.083178 1.284018 -0.528316 C -3.261773 1.990385 0.413366 H -3.669532 2.975721 0.626027 C -1.948481 1.683896 0.787498 C -1.025607 2.686709 1.453453 H -1.623548 3.500458 1.880661 C 0.022006 3.337254 0.509332 H 0.514178 4.149119 1.069024 H -0.479502 3.792029 -0.350245 C 1.160379 2.477315 -0.056300 C 2.010316 1.653146 0.912748 H 1.560781 0.654726 0.974718 H 1.917066 2.082359 1.919439 C 3.511934 1.530853 0.562534 H 4.012454 1.091719 1.437619 H 3.916968 2.547089 0.466549 C 3.940884 0.746075 -0.696220 H 5.007542 0.960217 -0.849573 H 3.415072 1.152208 -1.563901 C 3.795301 -0.797203 -0.667663 H 4.369265 -1.195436 -1.516074 H 4.272859 -1.195932 0.237422 O 1.408497 2.512143 -1.249169 H -0.510305 2.213687 2.300263 C -1.468176 0.403422 0.497956 H -0.464314 0.129984 0.792007 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24014430 Predicted Change= -1.071027D-07 Zero-point correction (ZPE)= -1075.8560 0.38407 Internal Energy (U)= -1075.8347 0.40537 Enthalpy (H)= -1075.8338 0.40631 Gibbs Free Energy (G)= -1075.9060 0.33414 ------------------------------------------------------------------------------ Frequencies -- 19.0002 37.8340 56.4379

5.2.79 Intdba Supporting Information: 030-GS-Ph-COin-C7-8-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24720199 Predicted Change= -5.207836D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00154 || 0.00180 [ YES ] 0.00154 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.639250 -1.877479 0.532298 H 2.178077 -1.944519 1.471258


S69

S69

C 0.252495 -2.036851 0.516567 O -0.521168 -2.285344 1.604302 C 0.101461 -2.299415 2.882212 H 0.589365 -1.340641 3.097728 H 0.836764 -3.110613 2.962062 H -0.702400 -2.469501 3.600086 C -0.433971 -1.844085 -0.699374 O -1.818158 -1.722424 -0.683622 C -2.274006 -0.445771 -0.350868 C 0.266931 -1.629001 -1.875750 H -0.293780 -1.493699 -2.795907 C 1.659606 -1.495501 -1.849741 H 2.197429 -1.282002 -2.769827 C 2.346737 -1.543542 -0.634655 C -3.661407 -0.261376 -0.451821 O -4.477490 -1.288254 -0.829860 H -3.911551 -2.068170 -0.963725 C -4.190133 0.996703 -0.171086 H -5.263164 1.137038 -0.259683 C -3.350808 2.053465 0.199235 H -3.786541 3.029276 0.400156 C -1.969189 1.872049 0.313318 C -1.031620 2.996723 0.718102 H -1.583639 3.942826 0.692618 C 0.225943 3.126130 -0.168784 H 0.599572 4.161568 -0.122871 H -0.015643 2.943353 -1.222689 C 1.427333 2.266191 0.247029 C 2.395631 1.901225 -0.872513 H 2.453425 2.760901 -1.555671 H 1.904875 1.109798 -1.456113 C 3.821733 1.491246 -0.459021 H 4.227324 2.287574 0.178683 H 4.437445 1.492167 -1.369772 C 4.047882 0.154716 0.278045 H 3.448719 0.142743 1.193606 H 5.099366 0.150665 0.595484 C 3.806569 -1.153536 -0.522292 H 4.247254 -1.062587 -1.523756 H 4.357559 -1.958409 -0.016825 O 1.600746 1.926901 1.405003 H -0.692761 2.858635 1.753459 C -1.449152 0.601205 0.037360 H -0.386832 0.427974 0.135543 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24720199 Predicted Change= -5.207836D-09 Zero-point correction (ZPE)= -1075.8631 0.38408 Internal Energy (U)= -1075.8417 0.40541 Enthalpy (H)= -1075.8408 0.40635 Gibbs Free Energy (G)= -1075.9131 0.33400 ------------------------------------------------------------------------------ Frequencies -- 17.6493 32.2510 50.4932

5.2.80 Intdbc Supporting Information: 030-GS-Ph-COout-C11-12out-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24756486 Predicted Change= -1.197892D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00181 || 0.00180 [ NO ] 0.00181 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.689655 -1.537903 0.793901 H 2.055450 -1.304895 1.787421 C 0.329579 -1.786666 0.597639 O -0.617742 -1.776720 1.570015 C -0.259953 -1.266466 2.853917 H 0.146721 -0.252446 2.772566

H 0.463427 -1.923056 3.354422 H -1.186893 -1.249263 3.429142 C -0.135977 -2.002443 -0.714991 O -1.510246 -1.995019 -0.953941 C -2.063000 -0.723432 -0.759964 C 0.757123 -2.091793 -1.773056 H 0.365619 -2.279795 -2.768490 C 2.118929 -1.852373 -1.560482 H 2.804862 -1.869966 -2.403600 C 2.584267 -1.506905 -0.287386 C -3.296060 -0.665088 -0.099275 O -3.924985 -1.802626 0.302024 H -3.295991 -2.532207 0.154712 C -3.859439 0.587808 0.153959 H -4.817095 0.631192 0.663619 C -3.173256 1.754008 -0.193005 H -3.612027 2.718233 0.053347 C -1.928456 1.698753 -0.833203 C -1.095136 2.932211 -1.115357 H -0.454214 2.753129 -1.987611 C -0.219273 3.385382 0.086948 H -0.860729 3.653777 0.931812 H 0.334588 4.287499 -0.215304 C 0.802239 2.379612 0.620979 C 1.879601 1.841273 -0.323512 H 2.046704 2.544778 -1.149703 H 1.457282 0.936327 -0.778385 C 3.204954 1.489735 0.380533 H 2.969374 1.059634 1.359318 H 3.742658 2.424083 0.585785 C 4.128979 0.537541 -0.416622 H 5.174733 0.809722 -0.224179 H 3.973274 0.683802 -1.494300 C 3.986185 -0.973620 -0.085032 H 4.696368 -1.529408 -0.710736 H 4.294047 -1.132209 0.956407 O 0.759535 2.025249 1.787571 H -1.742523 3.777953 -1.377830 C -1.408518 0.438573 -1.145172 H -0.462803 0.356797 -1.668683 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24756486 Predicted Change= -1.197892D-08 Zero-point correction (ZPE)= -1075.8632 0.38436 Internal Energy (U)= -1075.8420 0.40553 Enthalpy (H)= -1075.8410 0.40647 Gibbs Free Energy (G)= -1075.9120 0.33551 ------------------------------------------------------------------------------ Frequencies -- 37.4701 55.5816 59.9724

5.2.81 Intdca Supporting Information: 030-GS-Ph-C11-12in-7-8out-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23998131 Predicted Change= -2.257990D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00992 || 0.00180 [ NO ] 0.00992 || 0.00180 [ NO ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.340353 -2.104384 0.567171 H 1.707305 -2.356655 1.556655 C -0.033208 -2.132066 0.303656 O -0.999386 -2.459751 1.203908 C -0.601364 -2.801187 2.522791 H -0.083490 -1.967758 3.015498 H 0.048032 -3.686252 2.531169 H -1.523203 -3.023476 3.062714 C -0.485147 -1.709665 -0.961344 O -1.835968 -1.422742 -1.138918


S70

S70

C -2.207163 -0.197721 -0.580436 C 0.420676 -1.410812 -1.968107 H 0.036898 -1.093798 -2.933050 C 1.790344 -1.406315 -1.698456 H 2.486125 -1.104479 -2.475735 C 2.255702 -1.676197 -0.407562 C -3.581615 -0.013721 -0.374306 O -4.474560 -0.986656 -0.713039 H -3.956519 -1.753820 -1.014215 C -4.016236 1.185637 0.188418 H -5.081609 1.328405 0.341587 C -3.094345 2.166733 0.567464 H -3.457888 3.082570 1.027539 C -1.719941 1.981105 0.379383 C -0.703168 2.985441 0.896767 H -1.221486 3.931498 1.094513 C 0.500199 3.307403 -0.020425 H 0.999599 4.194498 0.402143 H 0.158837 3.590712 -1.020913 C 1.640171 2.296165 -0.221615 C 2.134231 1.476099 0.969515 H 1.481337 0.597858 1.056381 H 1.960050 2.055127 1.887028 C 3.619940 1.052097 0.930367 H 3.861731 0.630346 1.916773 H 4.220491 1.967181 0.842592 C 4.121546 0.077496 -0.158536 H 5.219052 0.101588 -0.113039 H 3.842631 0.467170 -1.140618 C 3.703780 -1.411552 -0.048121 H 4.356262 -1.985480 -0.720418 H 3.909916 -1.778779 0.966135 O 2.172717 2.217705 -1.315639 H -0.330010 2.651192 1.876532 C -1.299216 0.791876 -0.225158 H -0.249711 0.625310 -0.418564 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23998131 Predicted Change= -2.257990D-08 Zero-point correction (ZPE)= -1075.8559 0.38406 Internal Energy (U)= -1075.8345 0.40538 Enthalpy (H)= -1075.8336 0.40633 Gibbs Free Energy (G)= -1075.9061 0.33386 ------------------------------------------------------------------------------ Frequencies -- 13.1801 38.1489 54.0358

5.2.82 Intdcb Supporting Information: 030-GS2-Ph-C11-12-COin-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24756472 Predicted Change= -2.844846D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00197 || 0.00180 [ NO ] 0.00197 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.689707 -1.538428 0.793670 H 2.055601 -1.305886 1.787267 C 0.329608 -1.787140 0.597446 O -0.617569 -1.777501 1.569941 C -0.259667 -1.267312 2.853851 H 0.146876 -0.253233 2.772536 H 0.463848 -1.923858 3.354201 H -1.186535 -1.250258 3.429200 C -0.136082 -2.002437 -0.715212 O -1.510399 -1.994904 -0.953937 C -2.063064 -0.723326 -0.759902 C 0.756900 -2.091320 -1.773420 H 0.365309 -2.278943 -2.768893 C 2.118709 -1.851903 -1.560892

H 2.804564 -1.869127 -2.404078 C 2.584180 -1.506943 -0.287689 C -3.296159 -0.664945 -0.099253 O -3.925178 -1.802491 0.301906 H -3.296261 -2.532120 0.154507 C -3.859480 0.587947 0.154056 H -4.817155 0.631318 0.663683 C -3.173232 1.754157 -0.192796 H -3.611959 2.718380 0.053638 C -1.928416 1.698881 -0.832927 C -1.095057 2.932281 -1.115172 H -0.454199 2.753103 -1.987453 C -0.219078 3.385727 0.087005 H -0.860519 3.654281 0.931828 H 0.334676 4.287793 -0.215530 C 0.802417 2.380024 0.621176 C 1.879945 1.841797 -0.323235 H 2.047575 2.545718 -1.148957 H 1.457557 0.937228 -0.778770 C 3.204913 1.489363 0.381043 H 2.968734 1.058517 1.359338 H 3.742760 2.423380 0.587357 C 4.128918 0.537454 -0.416597 H 5.174705 0.809655 -0.224363 H 3.972958 0.683899 -1.494205 C 3.986162 -0.973779 -0.085308 H 4.696275 -1.529496 -0.711144 H 4.294083 -1.132546 0.956089 O 0.759433 2.025469 1.787683 H -1.742466 3.777993 -1.377697 C -1.408540 0.438687 -1.144982 H -0.462821 0.356914 -1.668472 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24756472 Predicted Change= -2.844846D-08 Zero-point correction (ZPE)= -1075.8632 0.38436 Internal Energy (U)= -1075.8420 0.40553 Enthalpy (H)= -1075.8410 0.40647 Gibbs Free Energy (G)= -1075.9120 0.33550 ------------------------------------------------------------------------------ Frequencies -- 37.4342 55.5577 59.9257

5.2.83 TSabc→abcd Supporting Information: 035-TS-C7-8-COin-C11-12out-Ph-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.17594531 Predicted Change= -4.572798D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00003 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00366 || 0.00180 [ NO ] 0.00366 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 2.348876 2.010518 0.035165 H 3.166771 2.699175 0.221140 C 2.658292 0.663574 -0.283888 O 3.926316 0.165932 -0.394737 C 5.017696 1.048298 -0.195561 H 5.020821 1.466431 0.820051 H 5.009740 1.871020 -0.922960 H 5.917159 0.446977 -0.340724 C 1.613702 -0.272563 -0.481786 O 1.843687 -1.632160 -0.786551 C 0.697438 -2.410289 -0.495769 C 0.328667 0.199992 -0.358378 H -0.512544 -0.450863 -0.397069 C 0.049215 1.516802 -0.129434 H -0.977109 1.782754 -0.110876 C 1.013200 2.462937 0.118444 C 0.709644 -3.091432 0.726167 O 1.865123 -3.249110 1.424759


S71

S71

H 2.559759 -2.786403 0.920245 C -0.504934 -3.537952 1.258327 H -0.496922 -4.062992 2.208345 C -1.704050 -3.160127 0.654386 H -2.637758 -3.369547 1.169779 C -1.733837 -2.466356 -0.565788 C -3.014624 -1.781713 -1.048575 H -3.294705 -2.157029 -2.042744 C -3.002209 -0.220328 -1.180396 H -3.917682 0.074658 -1.716699 H -2.187314 0.105769 -1.841456 C -2.939936 0.659767 0.088354 C -3.037421 2.204754 -0.127047 H -4.106386 2.421833 0.014374 H -2.829362 2.441619 -1.177746 C -2.207901 3.151580 0.829757 H -1.819298 2.551077 1.659562 H -2.920632 3.847772 1.283934 C -1.064585 4.025293 0.162524 H -1.281437 5.073489 0.399184 H -1.153920 3.948614 -0.929425 C 0.448561 3.817144 0.530055 H 1.009312 4.641317 0.068159 H 0.573452 3.947757 1.615653 O -2.870527 0.185756 1.203959 H -3.829775 -2.061617 -0.372486 C -0.500428 -2.237593 -1.198495 H -0.461136 -1.688990 -2.136068 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.17594531 Predicted Change= -4.572798D-08 Zero-point correction (ZPE)= -1075.7919 0.38399 Internal Energy (U)= -1075.7715 0.40436 Enthalpy (H)= -1075.7706 0.40530 Gibbs Free Energy (G)= -1075.8393 0.33655 ------------------------------------------------------------------------------ Frequencies -- -140.0030 44.2078 49.3847

5.2.84 TSabd→abdc Supporting Information: 035-TS-C7-8-COin-Ph-C11-12in-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.22620816 Predicted Change= -1.418517D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00093 || 0.00180 [ YES ] 0.00093 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.742345 -2.659114 0.311927 H 1.273768 -3.020785 1.186248 C -0.626996 -2.378819 0.400390 O -1.394065 -2.564623 1.506094 C -0.778571 -3.095434 2.670764 H 0.011473 -2.432101 3.046013 H -0.358033 -4.092129 2.484624 H -1.571770 -3.170208 3.416248 C -1.252832 -1.748721 -0.692984 O -2.477110 -1.114199 -0.504989 C -2.356081 0.249309 -0.215477 C -0.576922 -1.596874 -1.895295 H -1.098901 -1.134647 -2.728062 C 0.785156 -1.892673 -1.976027 H 1.330365 -1.666273 -2.888649 C 1.475280 -2.320894 -0.837646 C -3.537611 0.994851 -0.356179 O -4.702910 0.390702 -0.729250 H -4.506984 -0.554759 -0.850328 C -3.495259 2.367641 -0.122691 H -4.410389 2.939662 -0.241886 C -2.294329 2.991379 0.235172

H -2.284716 4.066607 0.396380 C -1.115025 2.256580 0.385458 C 0.209670 2.894224 0.775759 H 0.064906 3.968206 0.933377 C 1.346888 2.657450 -0.250358 H 1.536297 3.557010 -0.856129 H 1.054351 1.893745 -0.982380 C 2.688474 2.226932 0.346192 C 3.746134 1.694820 -0.635074 H 4.588841 2.398773 -0.636177 H 3.335116 1.679545 -1.651907 C 4.241480 0.279602 -0.243741 H 4.876994 0.359763 0.643632 H 4.875578 -0.101591 -1.053842 C 3.051078 -0.672370 0.032111 H 2.133148 -0.138104 -0.229131 H 2.968620 -0.861635 1.108006 C 2.961375 -2.035747 -0.720412 H 3.409561 -1.951911 -1.718114 H 3.507491 -2.819595 -0.181749 O 2.916922 2.264459 1.541212 H 0.548758 2.494509 1.739766 C -1.172821 0.871129 0.166653 H -0.275763 0.275584 0.288274 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.22620816 Predicted Change= -1.418517D-09 Zero-point correction (ZPE)= -1075.8426 0.38351 Internal Energy (U)= -1075.8219 0.40424 Enthalpy (H)= -1075.8210 0.40518 Gibbs Free Energy (G)= -1075.8918 0.33432 ------------------------------------------------------------------------------ Frequencies -- -103.7657 29.9819 38.7344

5.2.85 TSacb→acbd Supporting Information: 035-TS-C7-8-11-12in-COin-Ph-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.17594537 Predicted Change= -3.846756D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00016 || 0.00180 [ YES ] 0.00016 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 2.348085 2.011366 0.035205 H 3.165747 2.700330 0.221092 C 2.657924 0.664507 -0.283660 O 3.926096 0.167232 -0.394527 C 5.017202 1.050055 -0.195892 H 5.020583 1.468287 0.819681 H 5.008600 1.872703 -0.923364 H 5.916852 0.449089 -0.341367 C 1.613649 -0.272026 -0.481302 O 1.844351 -1.631503 -0.785986 C 0.698335 -2.410156 -0.495711 C 0.328470 0.200033 -0.357899 H -0.512505 -0.451139 -0.396361 C 0.048552 1.516841 -0.129386 H -0.977888 1.782484 -0.111030 C 1.012251 2.463357 0.118293 C 0.710484 -3.091441 0.726148 O 1.865840 -3.248800 1.425014 H 2.560496 -2.785939 0.920667 C -0.504074 -3.538386 1.257980 H -0.496123 -4.063519 2.207948 C -1.703163 -3.160804 0.653834 H -2.636921 -3.370511 1.169022 C -1.732891 -2.466960 -0.566296 C -3.013704 -1.782455 -1.049214 H -3.293269 -2.157357 -2.043686


S72

S72

C -3.001712 -0.220992 -1.180387 H -3.917104 0.073982 -1.716823 H -2.186731 0.105567 -1.841130 C -2.939773 0.658730 0.088630 C -3.038487 2.203714 -0.126266 H -4.107470 2.419884 0.016412 H -2.831747 2.441089 -1.177113 C -2.208861 3.151024 0.829974 H -1.819897 2.550889 1.659882 H -2.921697 3.847171 1.284056 C -1.066033 4.024966 0.162232 H -1.283215 5.073143 0.398670 H -1.155618 3.947988 -0.929679 C 0.447240 3.817504 0.529477 H 1.007571 4.641680 0.067070 H 0.572351 3.948657 1.614985 O -2.869711 0.184441 1.204077 H -3.829032 -2.062935 -0.373578 C -0.499412 -2.237795 -1.198728 H -0.460073 -1.689001 -2.136183 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.17594537 Predicted Change= -3.846756D-10 Zero-point correction (ZPE)= -1075.7919 0.38399 Internal Energy (U)= -1075.7715 0.40436 Enthalpy (H)= -1075.7706 0.40530 Gibbs Free Energy (G)= -1075.8393 0.33655 ------------------------------------------------------------------------------ Frequencies -- -139.9495 44.2077 49.3879

5.2.86 TSacd→acdb Supporting Information: 035-TS-C7-8-11-12out-Ph-COin-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23922534 Predicted Change= -7.888715D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00078 || 0.00180 [ YES ] 0.00078 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.006844 -2.314397 -0.480634 H -1.267683 -2.581472 -1.499200 C 0.330714 -2.125311 -0.128577 O 1.395967 -2.277253 -0.963483 C 1.152596 -2.596435 -2.326960 H 0.540438 -1.826867 -2.813660 H 0.659950 -3.571839 -2.427725 H 2.134811 -2.632051 -2.800148 C 0.636299 -1.669232 1.168168 O 1.924022 -1.200967 1.431548 C 2.142425 0.037993 0.801564 C -0.360065 -1.585002 2.130583 H -0.086855 -1.277563 3.135811 C -1.695237 -1.801300 1.774087 H -2.477096 -1.664756 2.516875 C -2.035063 -2.078808 0.445966 C 3.228975 0.126274 -0.076207 O 4.056362 -0.932138 -0.280357 H 3.626163 -1.699340 0.140007 C 3.425121 1.323800 -0.769995 H 4.260650 1.392762 -1.459872 C 2.522928 2.377133 -0.623068 H 2.672370 3.282909 -1.206460 C 1.423919 2.290682 0.245591 C 0.462969 3.461337 0.390334 H 0.848903 4.147372 1.158392 C -1.008323 3.157516 0.781187 H -1.483092 4.112044 1.028744 H -1.033385 2.535120 1.684329 C -1.894914 2.526033 -0.300960

C -1.790946 1.019333 -0.542491 H -1.524876 0.525358 0.394099 H -0.907457 0.889271 -1.184158 C -3.041159 0.376675 -1.188125 H -2.741642 -0.242377 -2.043246 H -3.651301 1.188063 -1.599343 C -3.907784 -0.474944 -0.231667 H -4.937477 -0.497965 -0.611867 H -3.958662 0.017720 0.749137 C -3.463885 -1.952985 -0.033705 H -4.152419 -2.425097 0.679079 H -3.582525 -2.485522 -0.986143 O -2.654013 3.228150 -0.945542 H 0.461253 4.039142 -0.542515 C 1.273886 1.109301 0.978556 H 0.447557 0.986792 1.668651 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23922534 Predicted Change= -7.888715D-10 Zero-point correction (ZPE)= -1075.8551 0.38402 Internal Energy (U)= -1075.8347 0.40446 Enthalpy (H)= -1075.8338 0.40540 Gibbs Free Energy (G)= -1075.9033 0.33582 ------------------------------------------------------------------------------ Frequencies -- -43.9421 31.9890 41.1205

5.2.87 TSadb→adbc Supporting Information: 035-TS2-C7-8-Ph-COin-C11-12out-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.22620814 Predicted Change= -1.503060D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00027 || 0.00180 [ YES ] 0.00027 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.742321 -2.659123 0.312020 H 1.273677 -3.020774 1.186391 C -0.627018 -2.378788 0.400377 O -1.394172 -2.564537 1.506031 C -0.778771 -3.095308 2.670769 H 0.011259 -2.431972 3.046043 H -0.358238 -4.092018 2.484703 H -1.572023 -3.170033 3.416200 C -1.252764 -1.748718 -0.693066 O -2.477050 -1.114183 -0.505185 C -2.356040 0.249311 -0.215609 C -0.576768 -1.596930 -1.895335 H -1.098680 -1.134724 -2.728155 C 0.785308 -1.892770 -1.975961 H 1.330587 -1.666417 -2.888553 C 1.475341 -2.320965 -0.837516 C -3.537614 0.994813 -0.356159 O -4.702920 0.390639 -0.729163 H -4.506971 -0.554811 -0.850293 C -3.495299 2.367589 -0.122582 H -4.410463 2.939581 -0.241657 C -2.294366 2.991347 0.235234 H -2.284785 4.066562 0.396531 C -1.115019 2.256588 0.385368 C 0.209658 2.894273 0.775665 H 0.064854 3.968251 0.933277 C 1.346892 2.657533 -0.250443 H 1.536331 3.557131 -0.856149 H 1.054351 1.893882 -0.982513 C 2.688458 2.226968 0.346120 C 3.746093 1.694742 -0.635112 H 4.588786 2.398713 -0.636357 H 3.335030 1.679310 -1.651925 C 4.241465 0.279589 -0.243596


S73

S73

H 4.876890 0.359879 0.643830 H 4.875652 -0.101668 -1.053597 C 3.051069 -0.672392 0.032260 H 2.133150 -0.138159 -0.229088 H 2.968532 -0.861577 1.108163 C 2.961430 -2.035822 -0.720181 H 3.409694 -1.952047 -1.717853 H 3.507498 -2.819636 -0.181420 O 2.916909 2.264553 1.541138 H 0.548752 2.494580 1.739680 C -1.172768 0.871152 0.166451 H -0.275673 0.275634 0.287942 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.22620814 Predicted Change= -1.503060D-10 Zero-point correction (ZPE)= -1075.8426 0.38351 Internal Energy (U)= -1075.8219 0.40424 Enthalpy (H)= -1075.8210 0.40518 Gibbs Free Energy (G)= -1075.8918 0.33432 ------------------------------------------------------------------------------ Frequencies -- -103.7772 29.9769 38.7210

5.2.88 TSadc→adcb Supporting Information: 035-TS-C7-8-Ph-C11-12in-COout-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23705850 Predicted Change= -3.963324D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00044 || 0.00180 [ YES ] 0.00044 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.732904 -2.130448 0.192628 H 2.438876 -2.395272 0.972468 C 0.360593 -2.328442 0.400303 O -0.192288 -2.846142 1.530733 C 0.677201 -3.289299 2.561662 H 1.275386 -2.463740 2.969735 H 1.349494 -4.081899 2.208538 H 0.029247 -3.686141 3.344879 C -0.537199 -1.884532 -0.586213 O -1.900130 -1.814713 -0.293003 C -2.316991 -0.502808 -0.045073 C -0.062630 -1.385687 -1.793733 H -0.783237 -1.071023 -2.543081 C 1.304764 -1.204864 -1.992959 H 1.660078 -0.759234 -2.918354 C 2.210272 -1.506486 -0.969261 C -3.574245 -0.142191 -0.545395 O -4.361138 -1.053228 -1.184572 H -3.862229 -1.889286 -1.206477 C -3.997287 1.180075 -0.394764 H -4.970549 1.460126 -0.785983 C -3.162717 2.123840 0.208939 H -3.499820 3.155196 0.281986 C -1.904268 1.767598 0.714180 C -0.950952 2.801027 1.289314 H -1.540994 3.647568 1.658933 C 0.087228 3.374865 0.278135 H 0.237325 4.443377 0.469429 H -0.334503 3.321080 -0.735328 C 1.519025 2.810424 0.165755 C 1.859182 1.417733 0.682461 H 1.213719 0.706694 0.156870 H 1.547997 1.365204 1.735671 C 3.344503 1.032846 0.547392 H 3.581757 0.279727 1.310725 H 3.940417 1.919470 0.787302 C 3.789890 0.504512 -0.835391 H 4.850647 0.748076 -0.976175

H 3.251495 1.044079 -1.623919 C 3.642679 -1.026036 -1.056700 H 4.060274 -1.268537 -2.042795 H 4.259373 -1.553202 -0.317149 O 2.364800 3.506933 -0.368429 H -0.436636 2.393793 2.168632 C -1.519839 0.427451 0.610448 H -0.570758 0.103674 1.015898 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23705850 Predicted Change= -3.963324D-10 Zero-point correction (ZPE)= -1075.8533 0.38373 Internal Energy (U)= -1075.8327 0.40430 Enthalpy (H)= -1075.8318 0.40525 Gibbs Free Energy (G)= -1075.9020 0.33504 ------------------------------------------------------------------------------ Frequencies -- -30.4168 26.1970 39.0381

5.2.89 TSbac→bacd Supporting Information: 035-TS-COin-C7-8out-11-12out-Ph-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.17594535 Predicted Change= -1.184426D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00191 || 0.00180 [ NO ] 0.00191 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 2.348625 2.010664 0.035118 H 3.166489 2.699359 0.221132 C 2.658081 0.663729 -0.283808 O 3.926115 0.166051 -0.394516 C 5.017449 1.048559 -0.195704 H 5.020810 1.466766 0.819878 H 5.009168 1.871227 -0.923156 H 5.916953 0.447347 -0.341068 C 1.613558 -0.272464 -0.481671 O 1.843931 -1.632021 -0.786261 C 0.697722 -2.410294 -0.495692 C 0.328523 0.199968 -0.358515 H -0.512627 -0.450963 -0.397240 C 0.048936 1.516797 -0.129731 H -0.977463 1.782675 -0.111254 C 1.012914 2.463023 0.118145 C 0.709721 -3.091109 0.726428 O 1.865050 -3.248513 1.425328 H 2.559832 -2.786055 0.920779 C -0.504946 -3.537545 1.258448 H -0.497113 -4.062344 2.208600 C -1.703953 -3.159861 0.654198 H -2.637753 -3.369130 1.169483 C -1.733523 -2.466444 -0.566179 C -3.014125 -1.781750 -1.049382 H -3.293446 -2.156584 -2.043948 C -3.001800 -0.220274 -1.180539 H -3.917185 0.074928 -1.716863 H -2.186809 0.106130 -1.841351 C -2.939631 0.659305 0.088550 C -3.037969 2.204353 -0.126042 H -4.106863 2.420753 0.016950 H -2.831423 2.441889 -1.176888 C -2.207920 3.151294 0.830189 H -1.818911 2.550925 1.659903 H -2.920466 3.847537 1.284574 C -1.065016 4.024987 0.162281 H -1.282037 5.073254 0.398456 H -1.154581 3.947757 -0.929612 C 0.448203 3.817226 0.529583 H 1.008723 4.641370 0.067350 H 0.573315 3.948142 1.615119


S74

S74

O -2.869775 0.184821 1.203934 H -3.829697 -2.062088 -0.373987 C -0.500004 -2.237859 -1.198735 H -0.460544 -1.689413 -2.136391 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.17594535 Predicted Change= -1.184426D-08 Zero-point correction (ZPE)= -1075.7919 0.38399 Internal Energy (U)= -1075.7715 0.40436 Enthalpy (H)= -1075.7706 0.40530 Gibbs Free Energy (G)= -1075.8393 0.33656 ------------------------------------------------------------------------------ Frequencies -- -139.9355 44.2037 49.4031

5.2.90 TSbad→badc Supporting Information: 035-TS-COin-C7-8out-Ph-C11-12out-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.22405061 Predicted Change= -7.689198D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00102 || 0.00180 [ YES ] 0.00102 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.751239 -2.620592 0.374641 H 1.306126 -2.920545 1.257589 C -0.618131 -2.344888 0.475849 O -1.359511 -2.466952 1.607379 C -0.714374 -2.920066 2.788943 H 0.076674 -2.228152 3.105711 H -0.288295 -3.922703 2.654742 H -1.491049 -2.955837 3.554444 C -1.270442 -1.782301 -0.638719 O -2.489090 -1.134263 -0.460662 C -2.352968 0.238427 -0.224195 C -0.623784 -1.701825 -1.863627 H -1.166976 -1.291534 -2.709938 C 0.736405 -2.000422 -1.958557 H 1.259862 -1.829526 -2.895649 C 1.454029 -2.350619 -0.810559 C -3.519890 0.993313 -0.423334 O -4.683155 0.390229 -0.804636 H -4.495112 -0.560969 -0.887901 C -3.465458 2.372990 -0.238232 H -4.369116 2.952075 -0.402404 C -2.267119 2.992368 0.134135 H -2.248324 4.071696 0.264360 C -1.102268 2.248258 0.343068 C 0.207159 2.883982 0.781636 H 0.052720 3.958329 0.928671 C 1.404609 2.659766 -0.177012 H 1.669571 3.584508 -0.710117 H 1.146732 1.949591 -0.975390 C 2.681737 2.144497 0.496173 C 3.887581 1.845656 -0.407912 H 4.761553 2.247970 0.113948 H 3.783767 2.400109 -1.347337 C 4.121994 0.322487 -0.725843 H 5.109733 0.021079 -0.359794 H 4.151171 0.203765 -1.815823 C 3.035682 -0.601379 -0.158234 H 2.070224 -0.127636 -0.356991 H 3.116536 -0.651583 0.933116 C 2.937969 -2.045375 -0.747301 H 3.375052 -2.077808 -1.752842 H 3.492617 -2.759976 -0.127951 O 2.755227 1.966208 1.698311 H 0.499572 2.484258 1.760600 C -1.170155 0.857946 0.164630 H -0.283675 0.257770 0.332529

------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.22405061 Predicted Change= -7.689198D-10 Zero-point correction (ZPE)= -1075.8406 0.38340 Internal Energy (U)= -1075.8197 0.40429 Enthalpy (H)= -1075.8188 0.40523 Gibbs Free Energy (G)= -1075.8907 0.33331 ------------------------------------------------------------------------------ Frequencies -- -152.8497 21.5333 29.8106

5.2.91 TSbca→bcad Supporting Information: 035-TS-COout-C11-12out-7-8-Ph-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.17594535 Predicted Change= -6.757185D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00099 || 0.00180 [ YES ] 0.00099 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 2.348319 2.011071 0.035245 H 3.166059 2.699911 0.221258 C 2.658023 0.664199 -0.283722 O 3.926147 0.166807 -0.394604 C 5.017336 1.049486 -0.195780 H 5.020712 1.467557 0.819858 H 5.008846 1.872250 -0.923122 H 5.916934 0.448455 -0.341308 C 1.613660 -0.272229 -0.481381 O 1.844172 -1.631744 -0.786073 C 0.698055 -2.410212 -0.495684 C 0.328523 0.200022 -0.358127 H -0.512529 -0.451052 -0.396561 C 0.048740 1.516867 -0.129661 H -0.977673 1.782641 -0.111480 C 1.012535 2.463244 0.118169 C 0.710129 -3.091411 0.726224 O 1.865463 -3.248886 1.425100 H 2.560193 -2.786198 0.920695 C -0.504478 -3.538203 1.258083 H -0.496577 -4.063310 2.208064 C -1.703527 -3.160514 0.653931 H -2.637308 -3.370109 1.169122 C -1.733173 -2.466707 -0.566221 C -3.013890 -1.782128 -1.049254 H -3.293360 -2.157018 -2.043757 C -3.001712 -0.220662 -1.180447 H -3.917051 0.074420 -1.716915 H -2.186669 0.105810 -1.841162 C -2.939725 0.659031 0.088588 C -3.038376 2.204037 -0.126183 H -4.107323 2.420287 0.016623 H -2.831719 2.441492 -1.177028 C -2.208525 3.151147 0.830069 H -1.819557 2.550822 1.659837 H -2.921188 3.847336 1.284356 C -1.065598 4.024984 0.162332 H -1.282728 5.073182 0.398717 H -1.155126 3.947952 -0.929578 C 0.447667 3.817397 0.529577 H 1.008048 4.641586 0.067254 H 0.572826 3.948417 1.615095 O -2.869649 0.184680 1.204009 H -3.829328 -2.062528 -0.373719 C -0.499688 -2.237718 -1.198680 H -0.460317 -1.688977 -2.136168 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm


S75

S75


5.2.92 TSbcd→bcda Supporting Information: 035-TS-COout-C11-12out-Ph-C7-8-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23867265 Predicted Change= -2.674063D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00059 || 0.00180 [ YES ] 0.00059 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.730142 -1.615659 0.717773 H 2.030457 -1.561156 1.758505 C 0.390850 -1.833987 0.397441 O -0.608106 -2.014638 1.300502 C -0.395590 -1.560736 2.637271 H -0.060601 -0.517423 2.641815 H 0.330266 -2.193555 3.163835 H -1.365397 -1.641490 3.130499 C 0.006289 -1.825225 -0.957263 O -1.349708 -1.831628 -1.275327 C -2.003587 -0.674653 -0.826605 C 0.963964 -1.732615 -1.958156 H 0.638117 -1.758915 -2.993817 C 2.307736 -1.531944 -1.622885 H 3.044622 -1.408093 -2.412554 C 2.690824 -1.406804 -0.283051 C -3.168371 -0.864886 -0.070496 O -3.632526 -2.115792 0.189860 H -2.939597 -2.732117 -0.109628 C -3.825860 0.256579 0.434170 H -4.723316 0.110970 1.027500 C -3.299359 1.532164 0.220520 H -3.808297 2.391074 0.651051 C -2.129755 1.727361 -0.522995 C -1.584289 3.117873 -0.779271 H -1.612785 3.308349 -1.859709 C -0.126935 3.471911 -0.294941 H -0.198751 4.305489 0.414478 H 0.450528 3.840568 -1.148021 C 0.691528 2.406276 0.447667 C 1.976241 1.916690 -0.223071 H 2.362205 2.693639 -0.895094 H 1.670649 1.087839 -0.878669 C 3.084366 1.445559 0.733760 H 2.630719 0.862350 1.540891 H 3.523245 2.330320 1.211897 C 4.202083 0.635636 0.029268 H 5.175185 0.897750 0.463453 H 4.255304 0.933186 -1.026870 C 4.064706 -0.911115 0.109385 H 4.836220 -1.360777 -0.528662 H 4.282880 -1.227966 1.136973 O 0.332819 1.986951 1.533643 H -2.275281 3.841013 -0.335455 C -1.505195 0.597753 -1.067720 H -0.604944 0.698762 -1.666640 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23867265 Predicted Change= -2.674063D-09 Zero-point correction (ZPE)= -1075.8548 0.38378

Internal Energy (U)= -1075.8341 0.40451 Enthalpy (H)= -1075.8332 0.40546 Gibbs Free Energy (G)= -1075.9035 0.33508 ------------------------------------------------------------------------------ Frequencies -- -151.5544 34.7373 47.2744

5.2.93 TSbda→bdac Supporting Information: 035-TS-COin-Ph-C7-8-11-12out-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.22405061 Predicted Change= -1.075769D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00057 || 0.00180 [ YES ] 0.00057 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.750979 -2.620663 0.374694 H 1.305822 -2.920637 1.257662 C -0.618375 -2.344863 0.475862 O -1.359790 -2.466860 1.607376 C -0.714722 -2.920036 2.788953 H 0.076372 -2.228189 3.105750 H -0.288719 -3.922706 2.654754 H -1.491421 -2.955754 3.554434 C -1.270619 -1.782238 -0.638725 O -2.489215 -1.134082 -0.460710 C -2.352958 0.238587 -0.224185 C -0.623924 -1.701841 -1.863620 H -1.167062 -1.291525 -2.709953 C 0.736246 -2.000541 -1.958514 H 1.259734 -1.829700 -2.895598 C 1.453822 -2.350760 -0.810492 C -3.519782 0.993610 -0.423378 O -4.683096 0.390664 -0.804744 H -4.495166 -0.560560 -0.887980 C -3.465199 2.373279 -0.238268 H -4.368783 2.952468 -0.402476 C -2.266808 2.992516 0.134159 H -2.247895 4.071841 0.264395 C -1.102053 2.248269 0.343148 C 0.207439 2.883828 0.781759 H 0.053102 3.958170 0.928947 C 1.404807 2.659607 -0.176988 H 1.669695 3.584321 -0.710181 H 1.146865 1.949375 -0.975290 C 2.682004 2.144407 0.496129 C 3.887720 1.845374 -0.408059 H 4.761797 2.247585 0.113705 H 3.783876 2.399828 -1.347480 C 4.121952 0.322177 -0.725969 H 5.109680 0.020668 -0.359975 H 4.151032 0.203413 -1.815948 C 3.035580 -0.601546 -0.158248 H 2.070153 -0.127755 -0.357040 H 3.116448 -0.651647 0.933106 C 2.937778 -2.045592 -0.747185 H 3.374917 -2.078154 -1.752698 H 3.492341 -2.760168 -0.127730 O 2.755636 1.966310 1.698286 H 0.499862 2.483948 1.760654 C -1.170093 0.857965 0.164702 H -0.283689 0.257686 0.332635 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.22405061 Predicted Change= -1.075769D-09 Zero-point correction (ZPE)= -1075.8406 0.38340 Internal Energy (U)= -1075.8197 0.40429 Enthalpy (H)= -1075.8188 0.40523 Gibbs Free Energy (G)= -1075.8907 0.33331 ------------------------------------------------------------------------------


S76

S76

Frequencies -- -152.8514 21.5389 29.8154

5.2.94 TSbdc→bdca Supporting Information: 035-TS-COout-Ph-C11-12in-7-8-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23867266 Predicted Change= -4.630087D-11 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00019 || 0.00180 [ YES ] 0.00019 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.730169 -1.615598 0.717677 H 2.030489 -1.561134 1.758409 C 0.390888 -1.833962 0.397330 O -0.608065 -2.014700 1.300373 C -0.395499 -1.561046 2.637217 H -0.060473 -0.517746 2.641942 H 0.330351 -2.193986 3.163645 H -1.365300 -1.641857 3.130453 C 0.006335 -1.825135 -0.957374 O -1.349665 -1.831565 -1.275424 C -2.003568 -0.674623 -0.826642 C 0.964012 -1.732445 -1.958259 H 0.638168 -1.758701 -2.993923 C 2.307783 -1.531763 -1.622975 H 3.044670 -1.407868 -2.412636 C 2.690851 -1.406668 -0.283130 C -3.168300 -0.864915 -0.070467 O -3.632368 -2.115844 0.189934 H -2.939419 -2.732131 -0.109591 C -3.825820 0.256515 0.434238 H -4.723235 0.110856 1.027617 C -3.299391 1.532129 0.220572 H -3.808345 2.391010 0.651144 C -2.129828 1.727382 -0.522993 C -1.584349 3.117906 -0.779198 H -1.612803 3.308428 -1.859629 C -0.127020 3.471868 -0.294794 H -0.198825 4.305381 0.414705 H 0.450486 3.840588 -1.147821 C 0.691395 2.406132 0.447712 C 1.976185 1.916700 -0.222994 H 2.362115 2.693724 -0.894950 H 1.670731 1.087836 -0.878640 C 3.084294 1.445624 0.733893 H 2.630631 0.862373 1.540991 H 3.523108 2.330399 1.212065 C 4.202089 0.635774 0.029441 H 5.175143 0.897846 0.463761 H 4.255429 0.933442 -1.026658 C 4.064717 -0.910993 0.109376 H 4.836247 -1.360570 -0.528711 H 4.282881 -1.227959 1.136929 O 0.332611 1.986608 1.533586 H -2.275347 3.841039 -0.335374 C -1.505244 0.597811 -1.067761 H -0.605008 0.698884 -1.666696 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23867266 Predicted Change= -4.630087D-11 Zero-point correction (ZPE)= -1075.8548 0.38378 Internal Energy (U)= -1075.8341 0.40451 Enthalpy (H)= -1075.8332 0.40546 Gibbs Free Energy (G)= -1075.9035 0.33508 ------------------------------------------------------------------------------ Frequencies -- -151.5654 34.7464 47.2957

5.2.95 TScab→cabd Supporting Information: 035-TS-C11-12in-7-8-COin-Ph-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.17594532 Predicted Change= -6.068020D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00072 || 0.00180 [ YES ] 0.00072 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -2.348956 -2.010370 0.035271 H -3.166917 -2.698991 0.221121 C -2.658222 -0.663378 -0.283598 O -3.926186 -0.165579 -0.394512 C -5.017655 -1.048011 -0.196144 H -5.021387 -1.466311 0.819400 H -5.009214 -1.870616 -0.923668 H -5.917057 -0.446706 -0.341747 C -1.613552 0.272729 -0.481177 O -1.843643 1.632278 -0.785971 C -0.697274 2.410409 -0.495697 C -0.328574 -0.199843 -0.357649 H 0.512681 0.450981 -0.396000 C -0.049220 -1.516785 -0.129230 H 0.977103 -1.782857 -0.110949 C -1.013308 -2.462916 0.118399 C -0.709138 3.091778 0.726116 O -1.864437 3.249696 1.424950 H -2.559278 2.787100 0.920614 C 0.505605 3.538259 1.257920 H 0.497873 4.063477 2.207842 C 1.704534 3.160146 0.653792 H 2.638384 3.369536 1.168943 C 1.733973 2.466193 -0.566284 C 3.014523 1.781175 -1.049167 H 3.294322 2.156038 -2.043588 C 3.001869 0.219733 -1.180433 H 3.917174 -0.075605 -1.716820 H 2.186794 -0.106458 -1.841245 C 2.939504 -0.660024 0.088543 C 3.037441 -2.205042 -0.126428 H 4.106342 -2.421782 0.015989 H 2.830345 -2.442263 -1.177241 C 2.207466 -3.151889 0.829962 H 1.818706 -2.551466 1.659755 H 2.920005 -3.848246 1.284185 C 1.064298 -4.025438 0.162285 H 1.281058 -5.073681 0.398814 H 1.153901 -3.948590 -0.929634 C -0.448887 -3.817328 0.529525 H -1.009580 -4.641221 0.067050 H -0.574073 -3.948519 1.615020 O 2.869651 -0.185753 1.204009 H 3.829926 2.061251 -0.373453 C 0.500403 2.237465 -1.198687 H 0.460836 1.688611 -2.136099 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.17594532 Predicted Change= -6.068020D-09 Zero-point correction (ZPE)= -1075.7919 0.38399 Internal Energy (U)= -1075.7715 0.40436 Enthalpy (H)= -1075.7706 0.40530 Gibbs Free Energy (G)= -1075.8393 0.33655 ------------------------------------------------------------------------------ Frequencies -- -139.9667 44.2068 49.3857

5.2.96 TScad→cadb Supporting Information: 035-TS-C11-12in-7-8-Ph-COout-Galeon.log


S77

S77

------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23705846 Predicted Change= 3.100442D-10 ============================================================================== Optimization completed on the basis of negligible forces. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00219 || 0.00180 [ NO ] 0.00219 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.732887 -2.130435 0.192635 H 2.438800 -2.395323 0.972507 C 0.360562 -2.328469 0.400176 O -0.192407 -2.846288 1.530510 C 0.677003 -3.289527 2.561470 H 1.275135 -2.463994 2.969676 H 1.349343 -4.082078 2.208328 H 0.028990 -3.686458 3.344593 C -0.537153 -1.884473 -0.586372 O -1.900108 -1.814677 -0.293271 C -2.316976 -0.502804 -0.045190 C -0.062488 -1.385506 -1.793804 H -0.783038 -1.070774 -2.543179 C 1.304919 -1.204649 -1.992901 H 1.660304 -0.758922 -2.918222 C 2.210345 -1.506358 -0.969156 C -3.574253 -0.142155 -0.545429 O -4.361157 -1.053138 -1.184669 H -3.862246 -1.889192 -1.206665 C -3.997307 1.180091 -0.394650 H -4.970586 1.460168 -0.785807 C -3.162731 2.123806 0.209122 H -3.499847 3.155148 0.282291 C -1.904256 1.767532 0.714279 C -0.950968 2.800911 1.289548 H -1.541050 3.647404 1.659220 C 0.087240 3.374890 0.278511 H 0.237639 4.443275 0.470316 H -0.334631 3.321758 -0.734924 C 1.518920 2.810218 0.165608 C 1.859346 1.417817 0.682895 H 1.213857 0.706469 0.157756 H 1.548422 1.365688 1.736202 C 3.344671 1.033026 0.547629 H 3.582057 0.279957 1.310973 H 3.940573 1.919688 0.787432 C 3.789921 0.504667 -0.835187 H 4.850646 0.748291 -0.976101 H 3.251404 1.044187 -1.623659 C 3.642758 -1.025892 -1.056443 H 4.060463 -1.268418 -2.042485 H 4.259376 -1.553033 -0.316809 O 2.364425 3.506402 -0.369430 H -0.436692 2.393614 2.168861 C -1.519812 0.427402 0.610390 H -0.570720 0.103591 1.015785 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23705846 Predicted Change= 3.100442D-10 Zero-point correction (ZPE)= -1075.8533 0.38373 Internal Energy (U)= -1075.8327 0.40430 Enthalpy (H)= -1075.8318 0.40525 Gibbs Free Energy (G)= -1075.9020 0.33504 ------------------------------------------------------------------------------ Frequencies -- -30.5921 26.1542 39.0281

5.2.97 TScba→cbad Supporting Information: 035-TS-C11-12in-Coin-C7-8-Ph-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ==============================================================================

# b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.17594541 Predicted Change= -6.831829D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00157 || 0.00180 [ YES ] 0.00157 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 2.347669 2.011760 0.035238 H 3.165201 2.700911 0.221007 C 2.657797 0.664977 -0.283717 O 3.926092 0.168049 -0.394749 C 5.016959 1.051131 -0.195920 H 5.020106 1.469311 0.819673 H 5.008240 1.873818 -0.923346 H 5.916779 0.450398 -0.341313 C 1.613716 -0.271753 -0.481411 O 1.844579 -1.631161 -0.786292 C 0.698780 -2.410051 -0.495782 C 0.328435 0.200027 -0.357843 H -0.512407 -0.451311 -0.396395 C 0.048247 1.516717 -0.129036 H -0.978243 1.782109 -0.110433 C 1.011754 2.463438 0.118566 C 0.711197 -3.091234 0.726133 O 1.866661 -3.248285 1.424892 H 2.561153 -2.785348 0.920389 C -0.503211 -3.538383 1.258140 H -0.495045 -4.063436 2.208149 C -1.702444 -3.161108 0.654094 H -2.636101 -3.370971 1.169402 C -1.732451 -2.467360 -0.566086 C -3.013486 -1.783188 -1.048893 H -3.293148 -2.158320 -2.043252 C -3.001829 -0.221754 -1.180340 H -3.917339 0.072947 -1.716724 H -2.186992 0.104835 -1.841244 C -2.939918 0.658241 0.088498 C -3.038813 2.203165 -0.126728 H -4.107884 2.419226 0.015458 H -2.831678 2.440361 -1.177536 C -2.209643 3.150704 0.829672 H -1.820846 2.550705 1.659756 H -2.922717 3.846792 1.283471 C -1.066734 4.024759 0.162191 H -1.284086 5.072909 0.398597 H -1.156069 3.947779 -0.929739 C 0.446489 3.817475 0.529767 H 1.006835 4.641762 0.067582 H 0.571310 3.948537 1.615321 O -2.869710 0.184199 1.204038 H -3.828644 -2.063725 -0.373076 C -0.499088 -2.237977 -1.198665 H -0.459960 -1.689221 -2.136152 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.17594541 Predicted Change= -6.831829D-09 Zero-point correction (ZPE)= -1075.7919 0.38399 Internal Energy (U)= -1075.7715 0.40436 Enthalpy (H)= -1075.7706 0.40530 Gibbs Free Energy (G)= -1075.8393 0.33655 ------------------------------------------------------------------------------ Frequencies -- -139.9947 44.1968 49.3847

5.2.98 TScbd→cbda Supporting Information: 035-TS-C11-12in-Coin-Ph-C7-8-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------


S78

S78

Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23867265 Predicted Change= -2.659676D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00058 || 0.00180 [ YES ] 0.00058 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.730139 -1.615674 0.717762 H 2.030456 -1.561185 1.758494 C 0.390846 -1.833998 0.397428 O -0.608109 -2.014662 1.300487 C -0.395590 -1.560781 2.637263 H -0.060601 -0.517469 2.641824 H 0.330266 -2.193609 3.163816 H -1.365397 -1.641543 3.130491 C 0.006285 -1.825217 -0.957275 O -1.349713 -1.831617 -1.275338 C -2.003588 -0.674644 -0.826607 C 0.963959 -1.732593 -1.958168 H 0.638110 -1.758880 -2.993829 C 2.307730 -1.531926 -1.622896 H 3.044614 -1.408064 -2.412564 C 2.690820 -1.406804 -0.283060 C -3.168371 -0.864878 -0.070495 O -3.632526 -2.115785 0.189858 H -2.939598 -2.732109 -0.109634 C -3.825858 0.256586 0.434177 H -4.723312 0.110975 1.027509 C -3.299356 1.532172 0.220529 H -3.808292 2.391082 0.651064 C -2.129753 1.727369 -0.522988 C -1.584283 3.117880 -0.779262 H -1.612773 3.308356 -1.859700 C -0.126931 3.471915 -0.294923 H -0.198751 4.305485 0.414505 H 0.450533 3.840584 -1.147997 C 0.691533 2.406275 0.447676 C 1.976257 1.916713 -0.223058 H 2.362231 2.693689 -0.895045 H 1.670679 1.087889 -0.878693 C 3.084366 1.445549 0.733775 H 2.630702 0.862325 1.540886 H 3.523248 2.330293 1.211939 C 4.202083 0.635630 0.029278 H 5.175185 0.897738 0.463466 H 4.255307 0.933189 -1.026857 C 4.064702 -0.911122 0.109382 H 4.836216 -1.360779 -0.528668 H 4.282874 -1.227981 1.136967 O 0.332818 1.986930 1.533642 H -2.275276 3.841022 -0.335450 C -1.505195 0.597763 -1.067718 H -0.604945 0.698773 -1.666638 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23867265 Predicted Change= -2.659676D-09 Zero-point correction (ZPE)= -1075.8548 0.38378 Internal Energy (U)= -1075.8341 0.40451 Enthalpy (H)= -1075.8332 0.40546 Gibbs Free Energy (G)= -1075.9035 0.33508 ------------------------------------------------------------------------------ Frequencies -- -151.5548 34.7359 47.2757

5.2.99 TScda→cdab Supporting Information: 035-TS1-C11-12out-Ph-C7-8-COin-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23890231 Predicted Change= -7.690626D-11

============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00038 || 0.00180 [ YES ] 0.00038 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.991844 -2.254840 0.523492 H 1.238302 -2.555519 1.536476 C -0.344111 -2.093290 0.146266 O -1.421969 -2.297803 0.951925 C -1.192233 -2.675333 2.301781 H -0.615425 -1.911321 2.838657 H -0.668269 -3.637638 2.365852 H -2.180041 -2.768918 2.755482 C -0.628380 -1.602800 -1.142894 O -1.913674 -1.140265 -1.419593 C -2.177676 0.062282 -0.748887 C 0.387929 -1.435906 -2.071952 H 0.129797 -1.080626 -3.065216 C 1.718995 -1.620698 -1.689389 H 2.514403 -1.423883 -2.403077 C 2.033522 -1.952238 -0.367674 C -3.455052 0.200388 -0.198148 O -4.385570 -0.783355 -0.335446 H -3.927274 -1.540525 -0.743248 C -3.749175 1.366844 0.512952 H -4.742062 1.478644 0.937926 C -2.768179 2.339575 0.706367 H -3.012246 3.223736 1.291315 C -1.475802 2.193170 0.178987 C -0.397916 3.223945 0.484732 H -0.845475 4.221840 0.389467 C 0.877285 3.215600 -0.382897 H 1.323426 4.217363 -0.351146 H 0.615582 3.063461 -1.438466 C 2.072775 2.279009 -0.096289 C 2.000899 1.202971 0.979887 H 1.227575 0.480835 0.693653 H 1.614834 1.674135 1.896133 C 3.344433 0.514722 1.296110 H 3.218263 -0.058595 2.225586 H 4.068163 1.306345 1.523715 C 3.984314 -0.399661 0.224889 H 5.056159 -0.466464 0.454652 H 3.916048 0.087043 -0.752508 C 3.460381 -1.856112 0.125160 H 4.126426 -2.402562 -0.556094 H 3.550672 -2.343651 1.104929 O 3.086012 2.451882 -0.752287 H -0.117394 3.144100 1.545370 C -1.212473 1.050716 -0.579315 H -0.238134 0.898463 -1.025307 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23890231 Predicted Change= -7.690626D-11 Zero-point correction (ZPE)= -1075.8551 0.38373 Internal Energy (U)= -1075.8347 0.40418 Enthalpy (H)= -1075.8337 0.40513 Gibbs Free Energy (G)= -1075.9034 0.33542 ------------------------------------------------------------------------------ Frequencies -- -30.7495 19.8205 39.9951

5.2.100 TScdb→cdba Supporting Information: 035-TS-C11-12out-Ph-COin-C7-8-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23867267 Predicted Change= -1.437660D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass?


S79

S79

Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00046 || 0.00180 [ YES ] 0.00046 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.730132 -1.615692 0.717716 H 2.030448 -1.561248 1.758450 C 0.390844 -1.834013 0.397365 O -0.608114 -2.014730 1.300409 C -0.395582 -1.560988 2.637228 H -0.060575 -0.517681 2.641893 H 0.330266 -2.193880 3.163712 H -1.365391 -1.641782 3.130451 C 0.006289 -1.825171 -0.957339 O -1.349710 -1.831569 -1.275399 C -2.003586 -0.674609 -0.826632 C 0.963966 -1.732491 -1.958224 H 0.638120 -1.758730 -2.993886 C 2.307736 -1.531830 -1.622937 H 3.044624 -1.407927 -2.412596 C 2.690816 -1.406766 -0.283093 C -3.168344 -0.864867 -0.070490 O -3.632477 -2.115782 0.189864 H -2.939549 -2.732094 -0.109654 C -3.825830 0.256582 0.434216 H -4.723265 0.110952 1.027570 C -3.299347 1.532177 0.220576 H -3.808279 2.391073 0.651142 C -2.129764 1.727398 -0.522967 C -1.584288 3.117916 -0.779201 H -1.612774 3.308424 -1.859633 C -0.126939 3.471912 -0.294849 H -0.198742 4.305463 0.414602 H 0.450542 3.840594 -1.147909 C 0.691506 2.406233 0.447708 C 1.976263 1.916744 -0.223015 H 2.362241 2.693769 -0.894944 H 1.670733 1.087944 -0.878706 C 3.084345 1.445549 0.733838 H 2.630648 0.862297 1.540913 H 3.523213 2.330277 1.212048 C 4.202084 0.635652 0.029351 H 5.175171 0.897738 0.463585 H 4.255350 0.933255 -1.026770 C 4.064694 -0.911101 0.109386 H 4.836214 -1.360735 -0.528672 H 4.282850 -1.228006 1.136960 O 0.332763 1.986800 1.533631 H -2.275277 3.841050 -0.335367 C -1.505211 0.597808 -1.067733 H -0.604972 0.698841 -1.666667 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23867267 Predicted Change= -1.437660D-09 Zero-point correction (ZPE)= -1075.8548 0.38378 Internal Energy (U)= -1075.8341 0.40451 Enthalpy (H)= -1075.8332 0.40546 Gibbs Free Energy (G)= -1075.9035 0.33508 ------------------------------------------------------------------------------ Frequencies -- -151.5626 34.7354 47.2875

5.2.101 TSdab→dabc Supporting Information: 035-TS-Ph-C7-8in-COin-C11-12in-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.22620811 Predicted Change= -2.962157D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00092 || 0.00180 [ YES ] 0.00092 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms)

Type X Y Z ------------------------------------------------------------------------------ C 0.742244 -2.659121 0.312104 H 1.273532 -3.020759 1.186521 C -0.627094 -2.378749 0.400367 O -1.394320 -2.564427 1.505985 C -0.778997 -3.095133 2.670793 H 0.011020 -2.431785 3.046073 H -0.358470 -4.091863 2.484819 H -1.572297 -3.169797 3.416182 C -1.252762 -1.748720 -0.693141 O -2.477047 -1.114136 -0.505382 C -2.356031 0.249336 -0.215706 C -0.576677 -1.596994 -1.895372 H -1.098526 -1.134810 -2.728244 C 0.785402 -1.892858 -1.975899 H 1.330740 -1.666562 -2.888470 C 1.475356 -2.321033 -0.837398 C -3.537630 0.994827 -0.356098 O -4.702965 0.390655 -0.729018 H -4.507024 -0.554792 -0.850181 C -3.495311 2.367592 -0.122462 H -4.410494 2.939577 -0.241421 C -2.294353 2.991349 0.235272 H -2.284772 4.066555 0.396627 C -1.114985 2.256594 0.385268 C 0.209702 2.894265 0.775535 H 0.064913 3.968248 0.933125 C 1.346901 2.657467 -0.250593 H 1.536317 3.557071 -0.856301 H 1.054352 1.893805 -0.982648 C 2.688512 2.227038 0.345952 C 3.746036 1.694520 -0.635230 H 4.588753 2.398464 -0.636698 H 3.334919 1.678839 -1.652017 C 4.241435 0.279495 -0.243328 H 4.876694 0.360053 0.644192 H 4.875815 -0.101857 -1.053135 C 3.051145 -0.672626 0.032544 H 2.133148 -0.138443 -0.228639 H 2.968788 -0.861922 1.108441 C 2.961466 -2.035998 -0.719988 H 3.409779 -1.952190 -1.717634 H 3.507459 -2.819888 -0.181262 O 2.917132 2.265065 1.540925 H 0.548813 2.494610 1.739560 C -1.172733 0.871172 0.166276 H -0.275619 0.275662 0.287653 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.22620811 Predicted Change= -2.962157D-09 Zero-point correction (ZPE)= -1075.8426 0.38351 Internal Energy (U)= -1075.8219 0.40424 Enthalpy (H)= -1075.8210 0.40518 Gibbs Free Energy (G)= -1075.8918 0.33432 ------------------------------------------------------------------------------ Frequencies -- -103.8517 29.9725 38.6842

5.2.102 TSdac→dacb Supporting Information: 035-TS-Ph-C7-8in-11-12in-COin-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23705850 Predicted Change= -3.112475D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00053 || 0.00180 [ YES ] 0.00053 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.732867 -2.130473 0.192636 H 2.438828 -2.395309 0.972482


S80

S80

C 0.360551 -2.328442 0.400298 O -0.192350 -2.846133 1.530723 C 0.677123 -3.289301 2.561662 H 1.275314 -2.463749 2.969740 H 1.349408 -4.081911 2.208547 H 0.029154 -3.686132 3.344873 C -0.537224 -1.884516 -0.586227 O -1.900156 -1.814678 -0.293030 C -2.317003 -0.502770 -0.045090 C -0.062635 -1.385680 -1.793741 H -0.783230 -1.071003 -2.543097 C 1.304764 -1.204882 -1.992955 H 1.660094 -0.759259 -2.918348 C 2.210258 -1.506521 -0.969250 C -3.574272 -0.142150 -0.545371 O -4.361189 -1.053184 -1.184523 H -3.862283 -1.889243 -1.206447 C -3.997306 1.180117 -0.394724 H -4.970580 1.460171 -0.785912 C -3.162716 2.123880 0.208955 H -3.499813 3.155237 0.282013 C -1.904251 1.767634 0.714155 C -0.950908 2.801056 1.289255 H -1.540926 3.647623 1.658853 C 0.087284 3.374834 0.278049 H 0.237346 4.443368 0.469242 H -0.334418 3.320933 -0.735421 C 1.519095 2.810415 0.165767 C 1.859214 1.417702 0.682442 H 1.213754 0.706687 0.156816 H 1.548000 1.365152 1.735643 C 3.344532 1.032792 0.547402 H 3.581764 0.279673 1.310743 H 3.940455 1.919408 0.787314 C 3.789926 0.504441 -0.835371 H 4.850692 0.747974 -0.976141 H 3.251557 1.044020 -1.623909 C 3.642677 -1.026104 -1.056678 H 4.060276 -1.268619 -2.042768 H 4.259350 -1.553284 -0.317120 O 2.364910 3.506946 -0.368325 H -0.436597 2.393834 2.168582 C -1.519830 0.427486 0.610407 H -0.570736 0.103708 1.015828 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23705850 Predicted Change= -3.112475D-10 Zero-point correction (ZPE)= -1075.8533 0.38373 Internal Energy (U)= -1075.8327 0.40430 Enthalpy (H)= -1075.8318 0.40525 Gibbs Free Energy (G)= -1075.9020 0.33504 ------------------------------------------------------------------------------ Frequencies -- -30.4025 26.1975 39.0381

5.2.103 TSdba→dbac Supporting Information: 035-TS-Ph-COin-C7-8-11-12out-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.22620813 Predicted Change= -5.551755D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00058 || 0.00180 [ YES ] 0.00058 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.742420 -2.659054 0.312155 H 1.273734 -3.020620 1.186586 C -0.626930 -2.378742 0.400411 O -1.394144 -2.564412 1.506037 C -0.778791 -3.095032 2.670869 H 0.011195 -2.431627 3.046112 H -0.358215 -4.091750 2.484939

H -1.572084 -3.169699 3.416263 C -1.252630 -1.748779 -0.693121 O -2.476947 -1.114266 -0.505364 C -2.356017 0.249220 -0.215723 C -0.576572 -1.597079 -1.895365 H -1.098448 -1.134957 -2.728254 C 0.785516 -1.892899 -1.975890 H 1.330841 -1.666612 -2.888471 C 1.475497 -2.320980 -0.837370 C -3.537653 0.994641 -0.356191 O -4.702930 0.390396 -0.729173 H -4.506921 -0.555038 -0.850330 C -3.495431 2.367408 -0.122555 H -4.410643 2.939337 -0.241567 C -2.294532 2.991240 0.235246 H -2.285025 4.066447 0.396595 C -1.115125 2.256561 0.385302 C 0.209511 2.894326 0.775604 H 0.064645 3.968299 0.933191 C 1.346775 2.657622 -0.250476 H 1.536243 3.557241 -0.856140 H 1.054253 1.894002 -0.982587 C 2.688321 2.227016 0.346105 C 3.745986 1.694882 -0.635145 H 4.588628 2.398914 -0.636395 H 3.334911 1.679436 -1.651952 C 4.241459 0.279760 -0.243647 H 4.876947 0.360094 0.643730 H 4.875605 -0.101481 -1.053688 C 3.051128 -0.672274 0.032311 H 2.133177 -0.138135 -0.229117 H 2.968586 -0.861332 1.108236 C 2.961573 -2.035790 -0.719978 H 3.409883 -1.952105 -1.717638 H 3.507638 -2.819533 -0.181111 O 2.916734 2.264498 1.541133 H 0.548613 2.494673 1.739634 C -1.172777 0.871130 0.166317 H -0.275634 0.275673 0.287747 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.22620813 Predicted Change= -5.551755D-10 Zero-point correction (ZPE)= -1075.8426 0.38351 Internal Energy (U)= -1075.8219 0.40424 Enthalpy (H)= -1075.8210 0.40518 Gibbs Free Energy (G)= -1075.8918 0.33432 ------------------------------------------------------------------------------ Frequencies -- -103.7695 29.9720 38.7273

5.2.104 TSdbc→dbca Supporting Information: 035-TS-Ph-COout-C11-12out-C7-8-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23867259 Predicted Change= -2.701249D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00156 || 0.00180 [ YES ] 0.00156 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.730212 -1.615327 0.717926 H 2.030536 -1.560540 1.758640 C 0.390922 -1.833755 0.397663 O -0.608023 -2.014182 1.300772 C -0.395422 -1.560120 2.637477 H -0.060339 -0.516838 2.641871 H 0.330394 -2.192940 3.164095 H -1.365224 -1.640725 3.130745 C 0.006360 -1.825324 -0.957044 O -1.349635 -1.831802 -1.275099 C -2.003564 -0.674790 -0.826550


S81

S81

C 0.964029 -1.732978 -1.957966 H 0.638172 -1.759534 -2.993618 C 2.307807 -1.532244 -1.622755 H 3.044690 -1.408600 -2.412460 C 2.690891 -1.406742 -0.282953 C -3.168420 -0.864985 -0.070543 O -3.632549 -2.115883 0.189897 H -2.939586 -2.732213 -0.109507 C -3.826002 0.256502 0.433948 H -4.723514 0.110916 1.027198 C -3.299518 1.532085 0.220239 H -3.808528 2.391017 0.650642 C -2.129834 1.727249 -0.523162 C -1.584332 3.117757 -0.779409 H -1.612692 3.308216 -1.859855 C -0.127069 3.471816 -0.294876 H -0.199025 4.305265 0.414678 H 0.450433 3.840643 -1.147859 C 0.691415 2.406104 0.447594 C 1.975960 1.916319 -0.223330 H 2.361623 2.692933 -0.895908 H 1.670266 1.087031 -0.878317 C 3.084467 1.445861 0.733405 H 2.631172 0.862998 1.540991 H 3.523358 2.330946 1.210935 C 4.202123 0.635788 0.028999 H 5.175245 0.897974 0.463096 H 4.255294 0.933170 -1.027191 C 4.064760 -0.910950 0.109382 H 4.836275 -1.360706 -0.528597 H 4.282953 -1.227617 1.137021 O 0.332843 1.986840 1.533644 H -2.275374 3.840910 -0.335686 C -1.505178 0.597615 -1.067725 H -0.604861 0.698625 -1.666548 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23867259 Predicted Change= -2.701249D-09 Zero-point correction (ZPE)= -1075.8548 0.38378 Internal Energy (U)= -1075.8341 0.40451 Enthalpy (H)= -1075.8332 0.40546 Gibbs Free Energy (G)= -1075.9035 0.33508 ------------------------------------------------------------------------------ Frequencies -- -151.5801 34.7743 47.2466

5.2.105 TSdca→dcab Supporting Information: 035-TS1-Ph-C11-12in-7-8out-COin-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23890233 Predicted Change= -2.394592D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00085 || 0.00180 [ YES ] 0.00085 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.991824 -2.254836 0.523484 H 1.238247 -2.555544 1.536468 C -0.344117 -2.093280 0.146213 O -1.422006 -2.297822 0.951826 C -1.192318 -2.675381 2.301682 H -0.615530 -1.911381 2.838596 H -0.668355 -3.637687 2.365750 H -2.180142 -2.768978 2.755345 C -0.628341 -1.602751 -1.142942 O -1.913626 -1.140209 -1.419672 C -2.177648 0.062310 -0.748921 C 0.388002 -1.435829 -2.071959 H 0.129906 -1.080522 -3.065221 C 1.719055 -1.620629 -1.689353 H 2.514487 -1.423790 -2.403006

C 2.033535 -1.952205 -0.367636 C -3.455005 0.200356 -0.198127 O -4.385493 -0.783417 -0.335416 H -3.927179 -1.540560 -0.743248 C -3.749139 1.366781 0.513021 H -4.742013 1.478536 0.938038 C -2.768166 2.339535 0.706430 H -3.012237 3.223670 1.291417 C -1.475803 2.193186 0.178999 C -0.397933 3.223976 0.484745 H -0.845495 4.221868 0.389461 C 0.877276 3.215626 -0.382866 H 1.323470 4.217364 -0.351016 H 0.615582 3.063599 -1.438452 C 2.072717 2.278949 -0.096329 C 2.000866 1.202987 0.979922 H 1.227541 0.480831 0.693737 H 1.614810 1.674203 1.896145 C 3.344402 0.514752 1.296182 H 3.218212 -0.058544 2.225668 H 4.068123 1.306383 1.523790 C 3.984323 -0.399652 0.225002 H 5.056154 -0.466471 0.454829 H 3.916120 0.087050 -0.752399 C 3.460375 -1.856095 0.125255 H 4.126441 -2.402554 -0.555971 H 3.550619 -2.343635 1.105028 O 3.085897 2.451705 -0.752447 H -0.117427 3.144148 1.545389 C -1.212468 1.050766 -0.579352 H -0.238139 0.898555 -1.025384 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23890233 Predicted Change= -2.394592D-10 Zero-point correction (ZPE)= -1075.8551 0.38373 Internal Energy (U)= -1075.8347 0.40418 Enthalpy (H)= -1075.8337 0.40513 Gibbs Free Energy (G)= -1075.9034 0.33542 ------------------------------------------------------------------------------ Frequencies -- -30.7632 19.8229 39.9962

5.2.106 TSdcb→dcba Supporting Information: 035-TS2-Ph-C11-12-COin-C7-8-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.23867265 Predicted Change= -2.595048D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00062 || 0.00180 [ YES ] 0.00062 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.730138 -1.615663 0.717767 H 2.030457 -1.561166 1.758496 C 0.390844 -1.833987 0.397436 O -0.608110 -2.014644 1.300497 C -0.395578 -1.560787 2.637279 H -0.060590 -0.517474 2.641854 H 0.330284 -2.193624 3.163812 H -1.365382 -1.641558 3.130516 C 0.006281 -1.825215 -0.957267 O -1.349718 -1.831615 -1.275328 C -2.003592 -0.674639 -0.826602 C 0.963953 -1.732601 -1.958162 H 0.638102 -1.758894 -2.993822 C 2.307726 -1.531936 -1.622894 H 3.044610 -1.408081 -2.412564 C 2.690818 -1.406804 -0.283060 C -3.168384 -0.864870 -0.070506 O -3.632550 -2.115776 0.189836 H -2.939623 -2.732103 -0.109653


S82

S82

C -3.825872 0.256595 0.434161 H -4.723334 0.110988 1.027480 C -3.299362 1.532180 0.220522 H -3.808299 2.391091 0.651052 C -2.129749 1.727374 -0.522981 C -1.584275 3.117885 -0.779249 H -1.612761 3.308366 -1.859686 C -0.126924 3.471912 -0.294907 H -0.198739 4.305479 0.414525 H 0.450546 3.840581 -1.147977 C 0.691539 2.406258 0.447678 C 1.976260 1.916702 -0.223064 H 2.362220 2.693669 -0.895069 H 1.670680 1.087863 -0.878682 C 3.084385 1.445556 0.733759 H 2.630736 0.862347 1.540889 H 3.523275 2.330310 1.211898 C 4.202090 0.635627 0.029257 H 5.175197 0.897735 0.463434 H 4.255304 0.933178 -1.026882 C 4.064704 -0.911122 0.109373 H 4.836214 -1.360789 -0.528676 H 4.282878 -1.227974 1.136960 O 0.332824 1.986894 1.533638 H -2.275272 3.841025 -0.335437 C -1.505190 0.597766 -1.067706 H -0.604933 0.698773 -1.666616 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.23867265 Predicted Change= -2.595048D-09 Zero-point correction (ZPE)= -1075.8548 0.38378 Internal Energy (U)= -1075.8341 0.40451 Enthalpy (H)= -1075.8332 0.40546 Gibbs Free Energy (G)= -1075.9035 0.33508 ------------------------------------------------------------------------------ Frequencies -- -151.5552 34.7373 47.2794

5.2.107 ent-Galeon Supporting Information: 040-GS2-C7-8-Ph-COin-C11-12out-Galeon.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H22O4 C1[X(C20H22O4)] #Atoms= 46 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1076.24995318 Predicted Change= -2.063757D-09 ============================================================================== Optimization completed on the basis of negligible forces. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00205 || 0.00180 [ NO ] 0.00205 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.798298 -1.511300 0.850016 H 2.249116 -1.294746 1.812147 C 0.416104 -1.695794 0.761274 O -0.447725 -1.626075 1.805295 C 0.019697 -1.059681 3.026607 H 0.441197 -0.061410 2.859189 H 0.766368 -1.703877 3.508638 H -0.858097 -0.985898 3.670396 C -0.157058 -1.907900 -0.508588 O -1.538391 -1.917903 -0.649148 C -2.171771 -0.688879 -0.464461 C 0.651084 -2.032494 -1.630747 H 0.177192 -2.208466 -2.591843 C 2.035652 -1.867984 -1.523689 H 2.654550 -1.933130 -2.414997 C 2.614879 -1.550347 -0.290357 C -3.566643 -0.742195 -0.350624 O -4.231021 -1.932772 -0.410414 H -3.556806 -2.631488 -0.473771 C -4.267052 0.451629 -0.177694 H -5.348954 0.407987 -0.096892 C -3.585723 1.668962 -0.099785 H -4.154300 2.583994 0.049039

C -2.189770 1.726593 -0.198091 C -1.439891 3.039313 -0.032025 H -2.049755 3.852182 -0.444209 C -0.042683 3.092415 -0.675747 H 0.268599 4.144549 -0.765661 H -0.060028 2.695796 -1.698109 C 1.070537 2.412918 0.131115 C 2.213705 1.809446 -0.679987 H 2.482677 2.511492 -1.482922 H 1.786227 0.941697 -1.203674 C 3.453832 1.392660 0.125811 H 3.129154 1.022481 1.103841 H 4.051400 2.288782 0.332523 C 4.333907 0.337854 -0.588568 H 5.392032 0.542485 -0.382324 H 4.216065 0.435753 -1.676432 C 4.067389 -1.137660 -0.181765 H 4.694318 -1.785531 -0.807896 H 4.406049 -1.279440 0.852255 O 1.034785 2.363872 1.348283 H -1.315841 3.257533 1.037248 C -1.502251 0.525949 -0.400451 H -0.425799 0.521247 -0.492156 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1076.24995318 Predicted Change= -2.063757D-09 Zero-point correction (ZPE)= -1075.8658 0.38406 Internal Energy (U)= -1075.8445 0.40537 Enthalpy (H)= -1075.8436 0.40631 Gibbs Free Energy (G)= -1075.9154 0.33447 ------------------------------------------------------------------------------ Frequencies -- 18.0543 43.9472 66.3762

5.3 Tautomers of 9’-

Desmethylgarugamblin I

5.3.1 C9-E-Tautomer Supporting Information: E1-9-desmethylgarugamblin-1-10-1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.02921951 Predicted Change= -4.939028D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00399 || 0.00180 [ NO ] 0.00399 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.654494 -2.218108 -1.379608 H -2.212847 -2.317919 -2.307680 C -0.260428 -2.254064 -1.416630 H 0.276122 -2.370396 -2.353133 C 0.454217 -2.032833 -0.241759 O 1.828762 -1.831260 -0.295635 C 2.196793 -0.494508 -0.239927 C -0.207636 -1.916370 0.980385 H 0.373254 -1.779567 1.887359 C -1.600014 -1.889084 1.002514 H -2.118151 -1.743556 1.947536 C -2.341814 -1.971848 -0.184104 C 3.511445 -0.202277 0.181461 O 4.301150 -1.275220 0.478311 C 5.632988 -1.021537 0.887099 H 5.668408 -0.438925 1.818114 H 6.201110 -0.490352 0.111239 H 6.084795 -2.000597 1.058001 C 3.896206 1.137044 0.271750 H 4.897854 1.392055 0.599669 C 2.995713 2.166770 -0.036604


S83

S83

H 3.323033 3.199050 0.063459 C 1.700816 1.883767 -0.468295 C 0.696550 2.975307 -0.793104 H 1.193144 3.948951 -0.712998 C -0.551294 2.984766 0.116539 H -1.022076 3.979995 0.076005 H -0.267146 2.828407 1.164375 C -1.654997 1.988975 -0.280304 C -2.592750 1.636550 0.796292 H -2.421878 2.138535 1.749614 C -3.607914 0.734139 0.745003 O -4.370877 0.477973 1.841602 H -4.062277 1.022908 2.585566 C -4.051379 -0.110100 -0.415795 H -3.530038 0.227759 -1.311559 H -5.128908 0.057698 -0.546073 C -3.815446 -1.637242 -0.196914 H -4.298499 -1.946135 0.736498 H -4.321041 -2.165778 -1.013385 O -1.730785 1.568359 -1.432643 H 0.351189 2.874878 -1.829021 C 1.328482 0.535838 -0.580780 H 0.337690 0.293068 -0.939993 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.02921951 Predicted Change= -4.939028D-08 Zero-point correction (ZPE)= -1074.6681 0.36108 Internal Energy (U)= -1074.6474 0.38172 Enthalpy (H)= -1074.6465 0.38266 Gibbs Free Energy (G)= -1074.7172 0.31194 ------------------------------------------------------------------------------ Frequencies -- 23.7068 39.0267 65.4128

5.3.2 C9-Z-Tautomer Supporting Information: Z1-9-desmethylgarugamblin-1-1-1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.04829684 Predicted Change= -2.150980D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00397 || 0.00180 [ NO ] 0.00397 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.828220 -1.916066 1.227748 H 2.409016 -1.752977 2.131688 C 0.435880 -1.882662 1.294259 H -0.077924 -1.701857 2.233285 C -0.304875 -2.000072 0.120069 O -1.678788 -1.812192 0.144768 C -2.116061 -0.501128 0.069522 C 0.327261 -2.268792 -1.093776 H -0.274149 -2.391662 -1.989224 C 1.719711 -2.315042 -1.142602 H 2.212460 -2.482267 -2.098367 C 2.490790 -2.080637 0.004724 C -3.515192 -0.315738 0.028160 O -4.271025 -1.451041 0.070426 C -5.679778 -1.307217 0.038245 H -6.017572 -0.827854 -0.890823 H -6.047596 -0.726294 0.895044 H -6.084512 -2.319819 0.088787 C -4.011259 0.985099 -0.058631 H -5.081124 1.155916 -0.100703 C -3.141819 2.082591 -0.101071 H -3.561266 3.083348 -0.170805 C -1.759329 1.910420 -0.050294 C -0.825171 3.108912 -0.046889 H -1.375660 3.975797 -0.429455 C 0.476339 2.950659 -0.865166 H 0.843937 3.954022 -1.125345

H 0.286209 2.430557 -1.810091 C 1.622124 2.282825 -0.111006 C 2.465835 1.336447 -0.801974 H 2.256415 1.083077 -1.833761 C 3.467003 0.668475 -0.138540 O 3.758446 0.913093 1.134555 H 3.102795 1.620899 1.432831 C 4.275775 -0.442115 -0.750848 H 5.343438 -0.215883 -0.635354 H 4.057766 -0.485907 -1.822278 C 3.979007 -1.826219 -0.094472 H 4.482477 -2.595684 -0.692676 H 4.426803 -1.846209 0.903845 O 1.817549 2.580627 1.089085 H -0.533571 3.358686 0.981861 C -1.264619 0.598710 0.031326 H -0.196445 0.429501 0.068158 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.04829684 Predicted Change= -2.150980D-08 Zero-point correction (ZPE)= -1074.6869 0.36137 Internal Energy (U)= -1074.6666 0.38168 Enthalpy (H)= -1074.6656 0.38263 Gibbs Free Energy (G)= -1074.7361 0.31210 ------------------------------------------------------------------------------ Frequencies -- 12.9469 45.8898 62.9991

5.3.3 C11-E-Tautomer Supporting Information: E2-9-Desmethylgarugamblin-1-1-1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.02373982 Predicted Change= -5.910884D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00060 || 0.00180 [ YES ] 0.00060 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.864789 -2.194871 -1.231982 H 2.427539 -2.170776 -2.161037 C 0.471383 -2.236138 -1.278049 H -0.059802 -2.249237 -2.224838 C -0.248973 -2.137557 -0.090452 O -1.622115 -1.932032 -0.127123 C -2.011547 -0.603612 -0.190324 C 0.405331 -2.156684 1.140663 H -0.180974 -2.118789 2.053676 C 1.798364 -2.139656 1.171205 H 2.306390 -2.099084 2.132499 C 2.546130 -2.081018 -0.014164 C -3.378349 -0.341591 0.034351 O -4.165089 -1.427880 0.288679 C -5.546555 -1.206156 0.507382 H -5.722756 -0.575293 1.389651 H -5.983927 -2.191929 0.677181 H -6.026473 -0.742229 -0.365256 C -3.817701 0.983655 -0.008410 H -4.861675 1.214200 0.172134 C -2.923706 2.026654 -0.272276 H -3.298165 3.047509 -0.295676 C -1.571627 1.775468 -0.512097 C -0.637996 2.923344 -0.871650 H -0.852734 3.238032 -1.902936 C 0.881739 2.662209 -0.809156 H 1.386974 3.563608 -1.186285 H 1.200791 1.859690 -1.476445 C 1.440356 2.390113 0.561642 C 2.482142 1.573247 0.881969 H 2.734698 1.483267 1.938575 C 3.271913 0.752637 -0.041122 O 3.213369 0.833769 -1.267420


S84

S84

C 4.211840 -0.281596 0.601657 H 4.069793 -0.305353 1.687655 H 5.246440 0.040226 0.420413 C 4.012881 -1.702668 0.009292 H 4.406307 -1.717256 -1.011171 H 4.609297 -2.410263 0.599872 O 0.785765 3.091763 1.518336 H -0.880021 3.786038 -0.241329 C -1.134178 0.445418 -0.463639 H -0.092499 0.217555 -0.642141 H 1.177934 2.897934 2.386650 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.02373982 Predicted Change= -5.910884D-09 Zero-point correction (ZPE)= -1074.6627 0.36097 Internal Energy (U)= -1074.6421 0.38162 Enthalpy (H)= -1074.6411 0.38257 Gibbs Free Energy (G)= -1074.7121 0.31161 ------------------------------------------------------------------------------ Frequencies -- 16.1452 44.1457 62.3556

5.3.4 C11-Z-Tautomer Supporting Information: Z2-9-Desmethylgarugamblin-1-4-1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.04771300 Predicted Change= -3.610126D-08 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00003 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00178 || 0.00180 [ YES ] 0.00178 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.586510 -2.350648 -1.110220 H -2.013107 -2.519026 -2.097053 C -0.202294 -2.284116 -0.969391 H 0.458966 -2.390413 -1.823882 C 0.343994 -2.014977 0.285736 O 1.709889 -1.792260 0.397977 C 2.118309 -0.482374 0.216563 C -0.472605 -1.921050 1.409680 H -0.023809 -1.741271 2.381765 C -1.858108 -1.971485 1.250481 H -2.500011 -1.821672 2.114544 C -2.435521 -2.132673 -0.014928 C 3.500953 -0.282791 0.007464 O 4.273935 -1.406234 0.004099 C 5.667056 -1.248894 -0.200183 H 6.089901 -2.254456 -0.160114 H 6.124493 -0.631266 0.584619 H 5.885228 -0.802580 -1.180115 C 3.963673 1.018941 -0.185332 H 5.018648 1.200326 -0.357427 C 3.077162 2.103669 -0.170770 H 3.469864 3.105421 -0.327467 C 1.713161 1.917705 0.048634 C 0.766233 3.101915 0.116948 H 0.439901 3.269558 1.151174 C -0.503908 3.020655 -0.774209 H -0.260645 2.606701 -1.757443 H -0.860845 4.048110 -0.934013 C -1.666474 2.265524 -0.183838 C -2.369170 1.284033 -0.844723 C -3.477587 0.614347 -0.209457 O -3.868635 0.925013 0.940215 C -4.171833 -0.535365 -0.928188 H -3.831712 -0.589356 -1.967952 H -5.249839 -0.333389 -0.935672 C -3.916603 -1.895644 -0.218038 H -4.427650 -1.884031 0.749662 H -4.373571 -2.689942 -0.821511 O -1.998429 2.655261 1.041130

H 1.320183 4.000684 -0.175974 C 1.251654 0.605360 0.241556 H 0.198069 0.428374 0.414170 H -2.795726 2.089516 1.303207 H -2.051910 0.981678 -1.834615 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.04771300 Predicted Change= -3.610126D-08 Zero-point correction (ZPE)= -1074.6862 0.36144 Internal Energy (U)= -1074.6659 0.38174 Enthalpy (H)= -1074.6650 0.38268 Gibbs Free Energy (G)= -1074.7353 0.31234 ------------------------------------------------------------------------------ Frequencies -- 17.4952 46.1431 57.5499

5.3.5 Keto-tautomer Supporting Information: diCO-9-Desmethylgarugamblin-1-1-1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.04370552 Predicted Change= -1.192546D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00217 || 0.00180 [ NO ] 0.00217 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.478814 -2.023012 1.098615 H 1.941549 -1.903159 2.073298 C 0.091482 -1.988981 0.985866 H -0.538846 -1.845407 1.858109 C -0.495114 -2.047083 -0.278148 O -1.853959 -1.784055 -0.412997 C -2.178423 -0.443911 -0.276746 C 0.281643 -2.273910 -1.411433 H -0.198244 -2.345009 -2.382569 C 1.671248 -2.306398 -1.284237 H 2.282324 -2.415173 -2.177763 C 2.290323 -2.116414 -0.041405 C -3.501788 -0.135958 0.104989 O -4.336463 -1.198672 0.289268 C -5.675702 -0.930410 0.665125 H -5.729811 -0.412539 1.632597 H -6.162462 -1.903817 0.749980 H -6.196530 -0.329202 -0.092515 C -3.848166 1.205893 0.275471 H -4.854363 1.471916 0.579458 C -2.902178 2.221685 0.082236 H -3.200259 3.255066 0.242987 C -1.598470 1.924528 -0.312434 C -0.564274 3.013434 -0.536083 H -0.293837 3.056854 -1.598825 C 0.742165 2.869956 0.278515 H 0.563492 2.378537 1.246210 H 1.142307 3.862568 0.534211 C 1.875492 2.123001 -0.413358 C 3.212718 2.050801 0.350316 H 3.197122 2.683532 1.240538 C 3.550856 0.618036 0.800072 O 3.435096 0.304814 1.968620 C 4.054256 -0.344009 -0.269386 H 5.139264 -0.168636 -0.350866 H 3.620751 -0.058493 -1.234118 C 3.775272 -1.832345 0.042749 H 4.329414 -2.444529 -0.678623 H 4.160231 -2.067425 1.039891 O 1.767739 1.616565 -1.514692 H -1.018056 3.979271 -0.288156 C -1.261424 0.576731 -0.503703 H -0.263585 0.322527 -0.836821 H 3.987856 2.404090 -0.340755 ------------------------------------------------------------------------------


S85

S85

Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.04370552 Predicted Change= -1.192546D-08 Zero-point correction (ZPE)= -1074.6836 0.36007 Internal Energy (U)= -1074.6627 0.38094 Enthalpy (H)= -1074.6618 0.38188 Gibbs Free Energy (G)= -1074.7335 0.31013 ------------------------------------------------------------------------------ Frequencies -- 24.3385 36.1757 51.6345

5.4 Model Systems for Classical and

Non-classical Hydrogen Bonding

5.4.1 Dimethoxybenzene-Enol

complex Supporting Information: Dimethoxy-enol-0002.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C11H16O3 C1[X(C11H16O3)] #Atoms= 30 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -654.415013741 Predicted Change= -4.298147D-07 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.02600 || 0.00180 [ NO ] 0.02600 || 0.00180 [ NO ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -0.200159 0.194624 -0.795496 H -1.079473 -0.294198 -1.201335 C -0.188332 1.599979 -0.690223 C -1.382468 2.403062 -1.152947 H -1.228552 3.473724 -0.983224 H -2.297760 2.107702 -0.624185 C 0.940377 2.211903 -0.157441 H 0.977417 3.294479 -0.065113 C 2.042331 1.453308 0.266212 H 2.907964 1.960676 0.677205 C 2.029701 0.066721 0.160928 O 3.045326 -0.763771 0.541096 C 4.211929 -0.171515 1.080697 H 4.696579 0.501826 0.360094 H 4.887509 -0.997469 1.312145 H 3.995762 0.388017 2.001495 C 0.884505 -0.573480 -0.380932 O 0.952372 -1.932790 -0.449382 C -0.147545 -2.626222 -1.019046 H -0.305449 -2.334577 -2.066697 H -1.074719 -2.455951 -0.458089 H 0.117431 -3.684676 -0.976423 H -1.572388 2.261771 -2.225038 O -3.406303 -1.362187 0.163245 C -3.415958 -0.287186 1.006526 H -2.413475 -0.093325 1.374861 H -4.309822 -1.516437 -0.159325 C -4.474347 0.450152 1.347490 H -4.358724 1.282226 2.031704 H -5.473669 0.248119 0.967639 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -654.415013741 Predicted Change= -4.298147D-07 Zero-point correction (ZPE)= -654.1633 0.25166 Internal Energy (U)= -654.1463 0.26866 Enthalpy (H)= -654.1454 0.26960 Gibbs Free Energy (G)= -654.2118 0.20318 ------------------------------------------------------------------------------ Frequencies -- 14.5819 23.7873 39.8291

5.4.2 Dimethoxybenzene-Ketone

complex Supporting Information: Dimethoxy-ketoneCoor-retry2.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C12H18O3 C1[X(C12H18O3)] #Atoms= 33 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -693.765726539 Predicted Change= -2.786894D-06 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.09243 || 0.00180 [ NO ] 0.09243 || 0.00180 [ NO ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -2.698408 -0.155777 -0.002332 O -3.609952 -1.173759 -0.037847 C -4.981351 -0.827913 -0.017535 C -3.009590 1.198455 0.048733 C -1.990816 2.162712 0.082580 C -0.652394 1.788546 0.065971 C 0.454536 2.817386 0.098099 C -0.335544 0.416788 0.014604 C -1.335170 -0.551500 -0.019581 O -1.119003 -1.896242 -0.069124 C 0.226114 -2.348633 -0.108909 H -5.260202 -0.216747 -0.887433 H -5.250861 -0.285170 0.899404 H -5.529377 -1.771868 -0.050861 H -4.044806 1.520745 0.063622 H -2.260604 3.215236 0.123255 H 0.052705 3.830910 0.200238 H 1.056341 2.792343 -0.820670 H 1.141317 2.644716 0.936599 H 0.708131 0.117642 0.006876 H 0.788607 -2.041532 0.780464 H 0.753215 -1.974603 -0.995576 H 0.169185 -3.438496 -0.149789 C 4.249232 -0.275800 0.014263 C 5.462983 -1.147347 0.284750 C 4.519495 1.146363 -0.443237 O 3.117016 -0.700596 0.158512 H 6.066781 -0.715992 1.093232 H 6.108197 -1.196671 -0.601170 H 5.144594 -2.153151 0.565285 H 5.060994 1.140724 -1.397853 H 5.157849 1.669515 0.279574 H 3.578922 1.687500 -0.561954 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -693.765726539 Predicted Change= -2.786894D-06 Zero-point correction (ZPE)= -693.4869 0.27881 Internal Energy (U)= -693.4678 0.29783 Enthalpy (H)= -693.4669 0.29878 Gibbs Free Energy (G)= -693.5404 0.22525 ------------------------------------------------------------------------------ Frequencies -- 9.2795 14.4361 25.0273

5.4.3 Dimethoxybenzene Supporting Information: Dimethoxybenzene.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc)


S86

S86

opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C9H12O2 C1[X(C9H12O2)] #Atoms= 23 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -500.605629944 Predicted Change= -7.681065D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00178 || 0.00180 [ YES ] 0.00178 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -0.907444 -0.428201 0.000123 O -2.255411 -0.211592 0.000253 C -3.103518 -1.345268 -0.000316 C -0.292686 -1.675684 0.000147 C 1.106238 -1.782430 0.000086 C 1.911484 -0.649614 0.000005 C 3.419519 -0.748251 -0.000136 C 1.287095 0.612861 0.000017 C -0.098523 0.737769 0.000052 O -0.778058 1.921088 0.000078 C -0.023383 3.119193 -0.000084 H -2.952493 -1.965679 0.893871 H -2.951870 -1.965204 -0.894723 H -4.123516 -0.955928 -0.000554 H -0.892563 -2.578783 0.000255 H 1.560217 -2.770102 0.000108 H 3.747990 -1.792488 0.000652 H 3.857128 -0.262151 0.881460 H 3.856878 -0.263639 -0.882679 H 1.906912 1.503571 -0.000022 H 0.609566 3.200267 -0.894436 H 0.609678 3.200452 0.894170 H -0.752857 3.931476 -0.000120 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -500.605629944 Predicted Change= -7.681065D-09 Zero-point correction (ZPE)= -500.4116 0.19402 Internal Energy (U)= -500.4003 0.20529 Enthalpy (H)= -500.3993 0.20623 Gibbs Free Energy (G)= -500.4487 0.15683 ------------------------------------------------------------------------------ Frequencies -- 60.7149 74.2209 93.6910

5.4.4 E-vinyligous Ester Supporting Information: E-vinyligous-ester.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C5H8O2 C1[X(C5H8O2)] #Atoms= 15 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -345.779510861 Predicted Change= -4.359668D-08 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00165 || 0.00180 [ YES ] 0.00165 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 2.578744 -0.700313 -0.000526 C 1.289633 0.112245 0.000186 C 0.055305 -0.685833 0.000134 C -1.210084 -0.203412 0.000041 O -2.221880 -1.114990 0.000502 C -1.626159 1.236010 -0.000610 O 1.337219 1.340749 0.000755 H 0.164745 -1.767144 0.000206 H -3.072521 -0.648222 -0.001208 H -0.748484 1.881498 -0.001236

H -2.237731 1.452173 0.886592 H -2.238484 1.451116 -0.887568 H 2.625105 -1.351616 0.881430 H 3.435937 -0.024515 -0.001017 H 2.624090 -1.351544 -0.882606 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -345.779510861 Predicted Change= -4.359668D-08 Zero-point correction (ZPE)= -345.6563 0.12316 Internal Energy (U)= -345.6481 0.13137 Enthalpy (H)= -345.6471 0.13231 Gibbs Free Energy (G)= -345.6889 0.09052 ------------------------------------------------------------------------------ Frequencies -- 76.9076 105.5217 158.7578

5.4.5 E-vinyligous Ester Rotation TS Supporting Information: E-vinyligous-ester-rotation-TS-04.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C5H8O2 C1[X(C5H8O2)] #Atoms= 15 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -345.761008877 Predicted Change= -1.274628D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00062 || 0.00180 [ YES ] 0.00062 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 2.023671 0.420954 1.041955 C 1.322761 -0.236702 -0.134581 C -0.049683 -0.797721 0.127003 C -1.189043 -0.103116 0.029096 O -2.376169 -0.742489 0.298368 C -1.305973 1.345795 -0.354511 O 1.862061 -0.342153 -1.220759 H -0.100814 -1.853806 0.384526 H -3.112798 -0.150682 0.084638 H -0.332759 1.788081 -0.577722 H -1.778020 1.928145 0.448575 H -1.928748 1.455799 -1.253242 H 1.424823 1.256494 1.425256 H 3.014452 0.774543 0.745980 H 2.116333 -0.296692 1.867343 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -345.761008877 Predicted Change= -1.274628D-09 Zero-point correction (ZPE)= -345.6393 0.12169 Internal Energy (U)= -345.6314 0.12952 Enthalpy (H)= -345.6305 0.13047 Gibbs Free Energy (G)= -345.6712 0.08973 ------------------------------------------------------------------------------ Frequencies -- -110.1431 117.0407 144.5322

5.4.6 E-vinyligous Ester-2 Supporting Information: E-vinyligous-ester-2.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C5H8O2 C1[X(C5H8O2)] #Atoms= 15


S87

S87

Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -345.769835610 Predicted Change= -2.248225D-07 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00008 || 0.00045 [ YES ] 0.00002 || 0.00030 [ YES ] Displ 0.00942 || 0.00180 [ NO ] 0.00942 || 0.00180 [ NO ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.712085 1.251857 0.000693 C 1.391495 -0.239194 -0.000055 C 0.014745 -0.761420 -0.001136 C -1.190459 -0.148582 -0.000179 O -2.281690 -0.974176 0.001222 C -1.537067 1.312852 -0.000559 O 2.318863 -1.042900 -0.000029 H -0.011950 -1.848030 -0.001611 H -3.093395 -0.444049 -0.000602 H -0.667394 1.963866 -0.005519 H -2.137593 1.555065 0.887268 H -2.144938 1.552161 -0.884215 H 1.309145 1.753381 -0.887154 H 2.798582 1.357734 0.002908 H 1.305362 1.753396 0.886794 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -345.769835610 Predicted Change= -2.248225D-07 Zero-point correction (ZPE)= -345.6465 0.12332 Internal Energy (U)= -345.6383 0.13147 Enthalpy (H)= -345.6374 0.13241 Gibbs Free Energy (G)= -345.6791 0.09072 ------------------------------------------------------------------------------ Frequencies -- 55.3754 120.9643 189.5659

5.4.7 Monomethoxybenzene-Enol

complex Supporting Information: Monomethoxy-enol-0004.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C10H14O2 C1[X(C10H14O2)] #Atoms= 26 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -539.897383406 Predicted Change= -3.518292D-09 ============================================================================== Optimization completed on the basis of negligible forces. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00189 || 0.00180 [ NO ] 0.00189 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.164407 1.651232 0.700398 H -1.293033 2.505422 1.362087 C 0.011470 1.531325 -0.043051 C 1.102443 2.575502 0.024910 H 2.093944 2.116938 -0.051467 H 1.056859 3.140562 0.962405 H 1.015833 3.301126 -0.795793 C 0.138922 0.408694 -0.879360 H 1.047436 0.281793 -1.463163 C -0.866652 -0.546491 -0.968538 H -0.764951 -1.413754 -1.614125 C -2.041865 -0.405667 -0.216549 O -2.971028 -1.398943 -0.371836 C -4.177758 -1.302750 0.363834 H -3.994783 -1.311062 1.447121 H -4.766789 -2.181141 0.092440 H -4.740376 -0.395698 0.103738 C -2.189084 0.701384 0.624221 H -3.083303 0.834808 1.222824

O 3.623890 -0.068290 -0.609840 H 4.572760 -0.002539 -0.808602 C 3.433768 -1.061352 0.309796 H 2.377513 -1.150885 0.544698 C 4.374157 -1.830002 0.860249 H 4.100963 -2.590903 1.581587 H 5.429084 -1.728057 0.614207 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -539.897383406 Predicted Change= -3.518292D-09 Zero-point correction (ZPE)= -539.6785 0.21879 Internal Energy (U)= -539.6641 0.23326 Enthalpy (H)= -539.6631 0.23420 Gibbs Free Energy (G)= -539.7246 0.17277 ------------------------------------------------------------------------------ Frequencies -- 13.3210 18.5512 36.4981

5.4.8 Monomethoxybenzene-Ketone

complex Supporting Information: Monomethoxy-ketoneCoor-retry3.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # opt=maxcycle=250 freq=noraman b3lyp/6-31g(d) geom=connectivity gfinput gfprint scf=(direct,tight,maxcycle=300,xqc) #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C11H16O2 C1[X(C11H16O2)] #Atoms= 29 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -579.248036541 Predicted Change= -3.760094D-07 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.04544 || 0.00180 [ NO ] 0.04544 || 0.00180 [ NO ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -3.183468 -1.095320 0.024177 C -3.246833 0.291866 0.028777 C -2.066151 1.049461 0.006140 O -2.232408 2.409798 0.012770 C -1.068250 3.216191 -0.010494 C -0.830841 0.398537 -0.020819 C -0.790506 -1.000196 -0.025019 C -1.952517 -1.773038 -0.002940 C -1.898063 -3.283827 -0.008583 H -4.109852 -1.666534 0.042071 H -4.199101 0.813517 0.049827 H -0.472188 3.042207 -0.916633 H -0.434901 3.039753 0.869532 H -1.418051 4.250796 -0.001718 H 0.105976 0.942537 -0.038738 H 0.185367 -1.478211 -0.046216 H -0.863638 -3.642434 -0.023462 H -2.407016 -3.705410 -0.885260 H -2.384017 -3.711230 0.878208 C 3.694528 -0.114147 -0.007762 C 4.414320 -1.450560 0.035657 C 4.564879 1.130378 0.023098 O 2.480773 -0.043300 -0.064764 H 5.018299 -1.530610 0.948247 H 5.105803 -1.541456 -0.811412 H 3.688743 -2.265585 0.004867 H 5.257309 1.134652 -0.828067 H 5.179303 1.146153 0.932031 H 3.938449 2.023802 -0.010711 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -579.248036541 Predicted Change= -3.760094D-07 Zero-point correction (ZPE)= -579.0021 0.24590 Internal Energy (U)= -578.9855 0.26248 Enthalpy (H)= -578.9846 0.26342 Gibbs Free Energy (G)= -579.0545 0.19344 ------------------------------------------------------------------------------


S88

S88

Frequencies -- 8.3136 12.6516 15.7523

5.4.9 Monomethoxybenzene Supporting Information: Monomethoxybenzene.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C8H10O C1[X(C8H10O)] #Atoms= 19 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -386.088781260 Predicted Change= -8.981614D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00145 || 0.00180 [ YES ] 0.00145 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.955208 -1.186306 0.000028 C -0.434009 -1.014100 0.000035 C -0.968133 0.276978 0.000029 O -2.303907 0.571875 -0.000007 C -3.224634 -0.505200 -0.000041 C -0.101048 1.380260 0.000019 C 1.273299 1.186490 0.000006 C 1.833986 -0.102444 0.000009 C 3.332690 -0.296589 -0.000042 H 1.355368 -2.197973 0.000033 H -1.077080 -1.886962 0.000056 H -3.113943 -1.133375 0.894324 H -3.113834 -1.133422 -0.894358 H -4.217842 -0.051846 -0.000114 H -0.530708 2.377422 0.000016 H 1.928935 2.054995 0.000009 H 3.799617 0.159674 -0.882337 H 3.596723 -1.359163 0.000800 H 3.799870 0.161124 0.881364 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -386.088781260 Predicted Change= -8.981614D-10 Zero-point correction (ZPE)= -385.9276 0.16109 Internal Energy (U)= -385.9189 0.16987 Enthalpy (H)= -385.9179 0.17081 Gibbs Free Energy (G)= -385.9621 0.12667 ------------------------------------------------------------------------------ Frequencies -- 30.0219 79.2854 152.7059

5.4.10 Z-vinyligous Ester Supporting Information: Z-vinyligous-ester-retry.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C5H8O2 C1[X(C5H8O2)] #Atoms= 15 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -345.799880297 Predicted Change= -1.821344D-09 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00326 || 0.00180 [ NO ] 0.00326 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z

------------------------------------------------------------------------------ C -2.553861 -0.757896 -0.000030 C -1.246980 0.008120 0.000086 C -0.008458 -0.735910 0.000028 C 1.199088 -0.083786 -0.000022 O 1.290062 1.241305 -0.000079 C 2.527034 -0.776281 0.000015 O -1.265729 1.257977 0.000071 H -0.028959 -1.819428 0.000067 H 0.339453 1.580012 -0.000039 H 3.104398 -0.474204 0.881593 H 3.104715 -0.473753 -0.881195 H 2.414191 -1.862581 -0.000268 H -3.391061 -0.057360 0.002102 H -2.618315 -1.408049 0.881025 H -2.620023 -1.404380 -0.883685 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -345.799880297 Predicted Change= -1.821344D-09 Zero-point correction (ZPE)= -345.6763 0.12353 Internal Energy (U)= -345.6684 0.13142 Enthalpy (H)= -345.6675 0.13237 Gibbs Free Energy (G)= -345.7095 0.09035 ------------------------------------------------------------------------------ Frequencies -- 24.9577 118.3899 152.2535

5.4.11 Z-vinyligous Ester Supporting Information: Z-vinyligous-ester-2.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C5H8O2 C1[X(C5H8O2)] #Atoms= 15 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -345.775367462 Predicted Change= -4.195762D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00003 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00281 || 0.00180 [ NO ] 0.00281 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.698612 1.204951 -0.000224 C -1.388218 -0.282346 -0.000004 C 0.008412 -0.761033 -0.000364 C 1.160072 -0.056756 -0.000160 O 1.159182 1.308924 0.000466 C 2.519664 -0.697201 0.000036 O -2.295930 -1.107552 0.000343 H 0.090950 -1.842910 -0.000518 H 2.073766 1.630221 -0.000920 H 3.092405 -0.392776 0.887295 H 3.093919 -0.390346 -0.885431 H 2.447735 -1.786270 -0.001602 H -2.783313 1.330781 -0.000329 H -1.264660 1.697114 -0.877532 H -1.264730 1.697511 0.876862 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -345.775367462 Predicted Change= -4.195762D-08 Zero-point correction (ZPE)= -345.6521 0.12320 Internal Energy (U)= -345.6439 0.13139 Enthalpy (H)= -345.6430 0.13233 Gibbs Free Energy (G)= -345.6845 0.09077 ------------------------------------------------------------------------------ Frequencies -- 74.8515 144.0268 170.6705


S89

S89

5.4.12 Z-vinyligous Ester Rotation TS Supporting Information: Z-vinyligous-ester-rotation-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C5H8O2 C1[X(C5H8O2)] #Atoms= 15 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -345.764699590 Predicted Change= -3.318610D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00011 || 0.00045 [ YES ] 0.00001 || 0.00030 [ YES ] Displ 0.00204 || 0.00180 [ NO ] 0.00204 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.983095 0.706937 0.906070 C -1.324099 -0.297669 -0.023164 C 0.079472 -0.713552 0.334919 C 1.173491 -0.017960 -0.007723 O 1.146159 1.138905 -0.746558 C 2.579707 -0.381235 0.360682 O -1.903225 -0.745344 -0.997419 H 0.191868 -1.647349 0.878012 H 0.271306 1.246055 -1.153607 H 3.048808 0.441302 0.914142 H 3.181064 -0.548027 -0.540739 H 2.605891 -1.281612 0.978653 H -2.981297 0.966249 0.544813 H -1.362429 1.608412 0.987951 H -2.051541 0.287353 1.917893 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -345.764699590 Predicted Change= -3.318610D-08 Zero-point correction (ZPE)= -345.6424 0.12223 Internal Energy (U)= -345.6348 0.12980 Enthalpy (H)= -345.6339 0.13074 Gibbs Free Energy (G)= -345.6741 0.09058 ------------------------------------------------------------------------------ Frequencies -- -117.3623 115.0701 141.2973

5.4.13 Enol Supporting Information: enol.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # opt=maxcycle=250 freq=noraman b3lyp/6-31g(d) geom=connectivity gfinput gfprint scf=(direct,tight,maxcycle=300,xqc) #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C2H4O C1[X(C2H4O)] #Atoms= 7 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -153.805679831 Predicted Change= -1.053677D-07 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00019 || 0.00045 [ YES ] 0.00005 || 0.00030 [ YES ] Displ 0.00096 || 0.00180 [ YES ] 0.00096 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ O -1.210174 -0.114783 -0.000195 H -1.119806 -1.082166 0.001204 C 0.035221 0.439174 0.000123 H -0.039238 1.523134 0.000188 C 1.204129 -0.203698 -0.000077 H 2.132933 0.354058 0.000167 H 1.271404 -1.289616 -0.000279 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis

Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -153.805679831 Predicted Change= -1.053677D-07 Zero-point correction (ZPE)= -153.7489 0.05674 Internal Energy (U)= -153.7453 0.06034 Enthalpy (H)= -153.7443 0.06129 Gibbs Free Energy (G)= -153.7733 0.03230 ------------------------------------------------------------------------------ Frequencies -- 483.9525 492.7736 714.3553

5.4.14 Ketone Supporting Information: ketone.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C3H6O C1[X(C3H6O)] #Atoms= 10 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -193.155694360 Predicted Change= -2.305275D-07 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00010 || 0.00045 [ YES ] 0.00002 || 0.00030 [ YES ] Displ 0.02155 || 0.00180 [ NO ] 0.02155 || 0.00180 [ NO ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.000003 0.184991 -0.000102 C -1.293305 -0.614623 -0.000282 C 1.293296 -0.614636 0.000214 O 0.000012 1.400702 0.000015 H -1.348881 -1.254089 0.889918 H -1.335705 -1.280123 -0.871748 H -2.148208 0.064257 -0.015670 H 1.347537 -1.257128 -0.887852 H 1.336960 -1.277187 0.873903 H 2.148235 0.064264 0.012346 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -193.155694360 Predicted Change= -2.305275D-07 Zero-point correction (ZPE)= -193.0716 0.08407 Internal Energy (U)= -193.0661 0.08949 Enthalpy (H)= -193.0652 0.09044 Gibbs Free Energy (G)= -193.1001 0.05551 ------------------------------------------------------------------------------ Frequencies -- 39.1260 135.1564 375.6030

5.5 C9-Z-9’-Desmethylgarugamblin I

5.5.1 C9-Z-9’-Desmethylgarugamblin I Supporting Information: Z-9-desmethylgarugamblin-a-mAnsa-a-GS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.04829684 Predicted Change= -2.204139D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00404 || 0.00180 [ NO ] 0.00404 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms)


S90

S90

Type X Y Z ------------------------------------------------------------------------------ C 1.828214 -1.916064 1.227751 H 2.409014 -1.752979 2.131686 C 0.435879 -1.882668 1.294256 H -0.077925 -1.701861 2.233282 C -0.304872 -2.000071 0.120065 O -1.678789 -1.812195 0.144763 C -2.116063 -0.501125 0.069523 C 0.327263 -2.268790 -1.093776 H -0.274148 -2.391656 -1.989230 C 1.719704 -2.315041 -1.142603 H 2.212461 -2.482267 -2.098369 C 2.490790 -2.080636 0.004723 C -3.515188 -0.315738 0.028158 O -4.271026 -1.451045 0.070426 C -5.679778 -1.307213 0.038248 H -6.017567 -0.827849 -0.890819 H -6.047593 -0.726289 0.895038 H -6.084514 -2.319807 0.088782 C -4.011263 0.985103 -0.058633 H -5.081117 1.155922 -0.100702 C -3.141819 2.082594 -0.101066 H -3.561265 3.083350 -0.170802 C -1.759329 1.910418 -0.050294 C -0.825165 3.108912 -0.046887 H -1.375656 3.975793 -0.429451 C 0.476340 2.950659 -0.865169 H 0.843941 3.954024 -1.125339 H 0.286207 2.430556 -1.810092 C 1.622126 2.282826 -0.111005 C 2.465836 1.336453 -0.801975 H 2.256415 1.083083 -1.833757 C 3.467003 0.668479 -0.138538 O 3.758445 0.913091 1.134551 H 3.102792 1.620896 1.432837 C 4.275778 -0.442116 -0.750847 H 5.343440 -0.215887 -0.635355 H 4.057760 -0.485908 -1.822273 C 3.979006 -1.826221 -0.094468 H 4.482470 -2.595688 -0.692678 H 4.426799 -1.846216 0.903845 O 1.817552 2.580621 1.089086 H -0.533569 3.358684 0.981868 C -1.264618 0.598710 0.031329 H -0.196451 0.429501 0.068159 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.04829684 Predicted Change= -2.204139D-08 Zero-point correction (ZPE)= -1074.6869 0.36137 Internal Energy (U)= -1074.6666 0.38168 Enthalpy (H)= -1074.6656 0.38263 Gibbs Free Energy (G)= -1074.7361 0.31210 ------------------------------------------------------------------------------ Frequencies -- 12.9134 45.8842 62.9978

5.5.2 TSa Supporting Information: Z-9-desmethylgarugamblin-a-mAnsa-b-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.03479430 Predicted Change= -4.072491D-11 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00010 || 0.00180 [ YES ] 0.00010 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.520583 -2.019343 0.998321 H 1.818534 -1.927529 2.038881 C 0.169356 -2.036645 0.673138

H -0.595115 -1.967773 1.440563 C -0.210241 -2.048556 -0.669070 O -1.542435 -1.838024 -1.006024 C -1.980072 -0.566169 -0.649667 C 0.743402 -2.195837 -1.674260 H 0.422286 -2.251027 -2.710065 C 2.097664 -2.178457 -1.332234 H 2.844715 -2.221236 -2.122517 C 2.503648 -2.018027 -0.001298 C -3.150695 -0.450259 0.124522 O -3.767459 -1.616896 0.466765 C -4.948021 -1.536852 1.247638 H -5.739906 -0.980925 0.727927 H -4.758692 -1.065659 2.221672 H -5.272984 -2.567332 1.402572 C -3.572683 0.829096 0.498457 H -4.463616 0.954857 1.103365 C -2.840634 1.958898 0.118644 H -3.189620 2.939277 0.433136 C -1.684611 1.852951 -0.656953 C -0.962106 3.087917 -1.160483 H -0.974624 3.059670 -2.257149 C 0.526850 3.366049 -0.727103 H 0.547668 4.320391 -0.189584 H 1.137801 3.496598 -1.626036 C 1.230552 2.383772 0.201651 C 2.308768 1.572490 -0.318243 H 2.532824 1.587579 -1.377945 C 3.063395 0.780487 0.514056 O 2.851432 0.737129 1.824934 H 2.047605 1.328861 1.988785 C 4.174015 -0.118146 0.036097 H 5.113443 0.191600 0.513276 H 4.291020 0.019983 -1.043275 C 3.920761 -1.626538 0.350904 H 4.660172 -2.214582 -0.206228 H 4.101788 -1.801083 1.416007 O 0.911221 2.352001 1.410416 H -1.558787 3.962403 -0.883425 C -1.277145 0.567992 -1.040262 H -0.383313 0.433290 -1.641824 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.03479430 Predicted Change= -4.072491D-11 Zero-point correction (ZPE)= -1074.6737 0.36108 Internal Energy (U)= -1074.6540 0.38071 Enthalpy (H)= -1074.6531 0.38165 Gibbs Free Energy (G)= -1074.7214 0.31330 ------------------------------------------------------------------------------ Frequencies -- -137.3834 20.9996 56.5111

5.5.3 TSbc Supporting Information: Z-9-desmethylgarugamblin-b-CO-b-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.02707033 Predicted Change= 2.367192D-10 ============================================================================== Optimization completed on the basis of negligible forces. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00203 || 0.00180 [ NO ] 0.00203 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.923907 -2.522944 1.382635 H 1.216535 -2.642318 2.423627 C -0.429349 -2.470038 1.058529 H -1.192867 -2.515257 1.828944 C -0.799031 -2.185514 -0.255778 O -2.087058 -1.728374 -0.516090 C -2.251146 -0.396148 -0.155543 C 0.155371 -2.160103 -1.268923


S91

S91

H -0.156647 -1.966648 -2.290601 C 1.507707 -2.234041 -0.930672 H 2.247889 -2.123667 -1.718334 C 1.911568 -2.315623 0.408604 C -3.561326 0.128258 -0.171259 O -4.544925 -0.724497 -0.576680 C -5.874472 -0.234574 -0.607500 H -5.977090 0.613543 -1.297900 H -6.216731 0.071794 0.390394 H -6.489711 -1.064065 -0.960892 C -3.749941 1.452424 0.232479 H -4.747415 1.877390 0.235976 C -2.671887 2.241756 0.660060 H -2.864182 3.258079 0.995496 C -1.374630 1.732690 0.669357 C -0.179657 2.528224 1.168263 H -0.555948 3.418272 1.684934 C 0.820736 3.007622 0.083619 H 1.125604 4.038320 0.297548 H 0.309413 3.062300 -0.886783 C 2.145400 2.289391 -0.199486 C 2.479730 0.950848 0.238385 H 1.799576 0.383367 0.856859 C 3.644524 0.358565 -0.213109 O 4.504493 1.019697 -0.975848 H 4.095864 1.944756 -1.110403 C 4.142347 -1.057615 0.005150 H 5.147189 -0.962521 0.438055 H 4.319758 -1.455890 -1.002736 C 3.346848 -2.074667 0.841024 H 3.921887 -3.011652 0.818722 H 3.341006 -1.757986 1.891025 O 2.944186 2.951147 -0.908666 H 0.353219 1.949659 1.934619 C -1.190394 0.415469 0.232809 H -0.188738 0.014866 0.217851 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.02707033 Predicted Change= 2.367192D-10 Zero-point correction (ZPE)= -1074.6664 0.36059 Internal Energy (U)= -1074.6469 0.38016 Enthalpy (H)= -1074.6459 0.38111 Gibbs Free Energy (G)= -1074.7141 0.31290 ------------------------------------------------------------------------------ Frequencies -- -43.1222 18.7132 61.2997

5.5.4 TSc Supporting Information: Z-9-desmethylgarugamblin-c-pAnsa-b-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.03929876 Predicted Change= 1.356044D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00047 || 0.00180 [ YES ] 0.00047 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.991940 -2.099729 -0.905435 H -2.730650 -2.115023 -1.702875 C -0.636593 -2.067141 -1.238608 H -0.311714 -2.056869 -2.274339 C 0.313718 -1.962424 -0.224634 O 1.645135 -1.744663 -0.549657 C 2.103025 -0.463959 -0.278013 C -0.072760 -2.009400 1.114696 H 0.685036 -1.959210 1.890366 C -1.428015 -2.030250 1.431154 H -1.730542 -2.005708 2.475840 C -2.408369 -2.016001 0.430338 C 3.492512 -0.299149 -0.105004

O 4.253333 -1.425127 -0.226199 C 5.654288 -1.296008 -0.060024 H 5.912036 -0.936736 0.945796 H 6.089954 -0.616712 -0.805299 H 6.065223 -2.297447 -0.201220 C 3.975000 0.978557 0.187772 H 5.037134 1.135230 0.339264 C 3.100226 2.064798 0.316326 H 3.508795 3.041088 0.566209 C 1.725760 1.913113 0.129645 C 0.778005 3.095361 0.244840 H 1.294931 3.903505 0.774695 C -0.559799 2.809981 0.963477 H -0.977047 3.764990 1.316482 H -0.407868 2.189611 1.853743 C -1.632410 2.193598 0.068676 C -2.594207 1.276687 0.632134 H -2.547572 1.025127 1.684779 C -3.493585 0.625568 -0.181729 O -3.564707 0.880164 -1.482715 H -2.861086 1.585900 -1.665942 C -4.471174 -0.441876 0.256219 H -5.098036 -0.648776 -0.615163 H -5.129234 -0.022526 1.026600 C -3.857712 -1.783299 0.800814 H -3.941159 -1.795860 1.892413 H -4.492435 -2.601075 0.437979 O -1.655997 2.506490 -1.145085 H 0.534646 3.481482 -0.753148 C 1.251289 0.631698 -0.183930 H 0.193911 0.473351 -0.349218 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.03929876 Predicted Change= 1.356044D-10 Zero-point correction (ZPE)= -1074.6784 0.36080 Internal Energy (U)= -1074.6588 0.38046 Enthalpy (H)= -1074.6578 0.38140 Gibbs Free Energy (G)= -1074.7266 0.31266 ------------------------------------------------------------------------------ Frequencies -- -82.0001 17.7631 47.1199

5.5.5 Inta Supporting Information: Z-9-desmethylgarugamblin-a-mAnsa-c-GS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.04449340 Predicted Change= -2.443017D-08 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00003 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00127 || 0.00180 [ YES ] 0.00127 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.733087 -1.887255 1.124432 H 2.264916 -1.619336 2.032852 C 0.341522 -1.916401 1.128819 H -0.222908 -1.674401 2.023971 C -0.339239 -2.162165 -0.062261 O -1.711418 -1.947382 -0.117205 C -2.064155 -0.612319 -0.238376 C 0.354821 -2.518974 -1.216807 H -0.198501 -2.742465 -2.123859 C 1.750640 -2.480862 -1.208191 H 2.293651 -2.690902 -2.127551 C 2.454710 -2.094669 -0.059848 C -3.392858 -0.266587 0.089673 O -4.195229 -1.290272 0.498516 C -5.536143 -0.984451 0.839919 H -6.087085 -0.569478 -0.015001 H -5.589639 -0.277173 1.678768 H -5.991370 -1.931049 1.136987 C -3.780151 1.070610 -0.022926


S92

S92

H -4.794110 1.362800 0.225717 C -2.873830 2.048756 -0.452932 H -3.209969 3.079936 -0.532036 C -1.562528 1.712961 -0.786093 C -0.564496 2.744420 -1.277844 H 0.013415 2.327465 -2.112594 C 0.404376 3.310451 -0.210084 H -0.159264 3.714564 0.636307 H 0.946681 4.155126 -0.663087 C 1.473737 2.399447 0.385336 C 2.271764 1.526552 -0.448649 H 2.075624 1.452686 -1.511018 C 3.264132 0.749211 0.102068 O 3.563011 0.798587 1.395607 H 2.913967 1.466571 1.796080 C 4.082836 -0.253910 -0.667177 H 5.142143 0.026607 -0.594382 H 3.798770 -0.211742 -1.723383 C 3.915122 -1.709886 -0.130704 H 4.475149 -2.378655 -0.795177 H 4.374373 -1.773275 0.860636 O 1.682849 2.480880 1.617379 H -1.113653 3.598400 -1.692513 C -1.179820 0.368776 -0.675216 H -0.167087 0.087576 -0.933911 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.04449340 Predicted Change= -2.443017D-08 Zero-point correction (ZPE)= -1074.6832 0.36124 Internal Energy (U)= -1074.6630 0.38144 Enthalpy (H)= -1074.6621 0.38238 Gibbs Free Energy (G)= -1074.7318 0.31269 ------------------------------------------------------------------------------ Frequencies -- 21.1082 47.9030 69.7017

5.5.6 Intc Supporting Information: Z-9-desmethylgarugamblin-c-pAnsa-c-GS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.04022374 Predicted Change= -6.009342D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00003 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00830 || 0.00180 [ NO ] 0.00830 || 0.00180 [ NO ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.834913 -2.216223 -0.891118 H -2.535770 -2.240304 -1.721897 C -0.468034 -2.169478 -1.167018 H -0.100588 -2.150355 -2.188280 C 0.435765 -2.045816 -0.113970 O 1.768680 -1.774215 -0.383145 C 2.144716 -0.453168 -0.190913 C -0.004693 -2.113692 1.207264 H 0.718809 -2.053175 2.014387 C -1.372935 -2.147627 1.466046 H -1.719111 -2.120749 2.497241 C -2.309562 -2.124420 0.424396 C 3.530170 -0.191292 -0.157789 O 4.349789 -1.269434 -0.323741 C 5.748433 -1.045238 -0.300300 H 6.078057 -0.637969 0.665405 H 6.063122 -0.363795 -1.102370 H 6.209908 -2.022281 -0.455561 C 3.951847 1.123119 0.051462 H 5.010811 1.351938 0.094010 C 3.022778 2.154896 0.232307 H 3.386497 3.163638 0.412889 C 1.650398 1.908094 0.186236 C 0.648922 3.037868 0.364494 H 1.143098 3.847572 0.913350

C -0.663900 2.669239 1.099373 H -1.051150 3.576859 1.583624 H -0.480888 1.939801 1.895308 C -1.784868 2.195453 0.178034 C -2.588038 1.054642 0.549432 H -2.367145 0.522595 1.464544 C -3.538841 0.560961 -0.314876 O -3.819958 1.174072 -1.458529 H -3.203846 1.976934 -1.500813 C -4.365581 -0.693914 -0.131425 H -4.579953 -1.053447 -1.143806 H -5.340703 -0.404715 0.285686 C -3.769431 -1.838760 0.723999 H -3.867680 -1.597062 1.788706 H -4.397802 -2.724345 0.557602 O -1.985658 2.825633 -0.886506 H 0.367606 3.459132 -0.609721 C 1.232606 0.588331 -0.040230 H 0.174871 0.363422 -0.087357 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.04022374 Predicted Change= -6.009342D-08 Zero-point correction (ZPE)= -1074.6790 0.36115 Internal Energy (U)= -1074.6587 0.38146 Enthalpy (H)= -1074.6578 0.38241 Gibbs Free Energy (G)= -1074.7282 0.31197 ------------------------------------------------------------------------------ Frequencies -- 19.3929 32.4156 59.3211

5.5.7 TSa→ab Supporting Information: Z-9-desmethylgarugamblin-a-mAnsa-CO-d-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.03467044 Predicted Change= 9.382929D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00127 || 0.00180 [ YES ] 0.00127 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.118859 -2.056804 1.361281 H 1.564886 -1.824079 2.325128 C -0.260917 -1.944627 1.202926 H -0.893779 -1.616300 2.021587 C -0.824013 -2.147800 -0.057318 O -2.143784 -1.774120 -0.288855 C -2.318090 -0.396905 -0.326403 C -0.041328 -2.611552 -1.113162 H -0.504141 -2.799208 -2.077141 C 1.338681 -2.727572 -0.936294 H 1.954842 -3.028646 -1.780963 C 1.947461 -2.377076 0.277665 C -3.594949 0.120210 -0.023208 O -4.567265 -0.796191 0.245876 C -5.863371 -0.314795 0.558591 H -6.291926 0.262055 -0.271993 H -5.856301 0.308715 1.462941 H -6.475477 -1.200940 0.735913 C -3.759442 1.508664 -0.008624 H -4.728903 1.934068 0.225524 C -2.681437 2.369692 -0.261084 H -2.840791 3.443769 -0.204647 C -1.420795 1.863183 -0.573637 C -0.192008 2.733045 -0.762934 H 0.377841 2.375725 -1.629502 C 0.745366 2.777234 0.497037 H 0.285683 2.189405 1.301244 H 0.843501 3.803898 0.859449 C 2.169013 2.259254 0.304934 C 2.393216 0.868257 -0.021875


S93

S93

H 1.551707 0.207347 -0.153926 C 3.666712 0.357946 -0.121859 O 4.738059 1.123536 0.063211 H 4.381858 2.049351 0.262542 C 4.025474 -1.066694 -0.496254 H 5.118229 -1.125637 -0.476450 H 3.718493 -1.229954 -1.537543 C 3.450436 -2.219537 0.376020 H 3.952752 -3.138707 0.046982 H 3.741587 -2.061600 1.420578 O 3.122961 3.052657 0.473876 H -0.498364 3.756654 -1.002321 C -1.279004 0.471383 -0.636828 H -0.320634 0.053983 -0.914124 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.03467044 Predicted Change= 9.382929D-10 Zero-point correction (ZPE)= -1074.6734 0.36122 Internal Energy (U)= -1074.6538 0.38078 Enthalpy (H)= -1074.6529 0.38172 Gibbs Free Energy (G)= -1074.7208 0.31386 ------------------------------------------------------------------------------ Frequencies -- -41.2653 30.5460 61.3273

5.5.8 TSa→ac Supporting Information: Z-9-desmethylgarugamblin-a-mAnsa-pAnsa-d-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.03467045 Predicted Change= -1.253798D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00064 || 0.00180 [ YES ] 0.00064 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.118720 -2.056884 1.361302 H 1.564691 -1.824165 2.325176 C -0.261044 -1.944698 1.202864 H -0.893954 -1.616370 2.021487 C -0.824061 -2.147842 -0.057420 O -2.143795 -1.774094 -0.289051 C -2.318056 -0.396867 -0.326499 C -0.041319 -2.611604 -1.113217 H -0.504074 -2.799243 -2.077227 C 1.338678 -2.727639 -0.936264 H 1.954890 -3.028708 -1.780898 C 1.947383 -2.377144 0.277731 C -3.594894 0.120248 -0.023228 O -4.567219 -0.796154 0.245822 C -5.863305 -0.314756 0.558615 H -6.291879 0.262159 -0.271914 H -5.856193 0.308690 1.463008 H -6.475420 -1.200902 0.735897 C -3.759365 1.508703 -0.008538 H -4.728811 1.934106 0.225669 C -2.681354 2.369725 -0.260968 H -2.840690 3.443801 -0.204452 C -1.420727 1.863223 -0.573598 C -0.191962 2.733120 -0.762878 H 0.377905 2.375810 -1.629438 C 0.745424 2.777339 0.497087 H 0.285715 2.189596 1.301340 H 0.843631 3.804025 0.859417 C 2.169034 2.259269 0.304961 C 2.393168 0.868214 -0.021653 H 1.551622 0.207295 -0.153454 C 3.666655 0.357898 -0.121793 O 4.738025 1.123523 0.062997 H 4.381851 2.049362 0.262276

C 4.025406 -1.066765 -0.496116 H 5.118160 -1.125712 -0.476296 H 3.718450 -1.230048 -1.537409 C 3.450348 -2.219582 0.376167 H 3.952698 -3.138754 0.047183 H 3.741439 -2.061613 1.420737 O 3.123018 3.052681 0.473665 H -0.498347 3.756718 -1.002271 C -1.278953 0.471423 -0.636896 H -0.320589 0.054028 -0.914232 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.03467045 Predicted Change= -1.253798D-10 Zero-point correction (ZPE)= -1074.6734 0.36122 Internal Energy (U)= -1074.6538 0.38078 Enthalpy (H)= -1074.6529 0.38172 Gibbs Free Energy (G)= -1074.7208 0.31386 ------------------------------------------------------------------------------ Frequencies -- -41.2412 30.5513 61.3231

5.5.9 TSc→ca Supporting Information: Z-9-desmethylgarugamblin-c-pAnsa-mAnsa-d-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.03479427 Predicted Change= -4.289358D-09 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00180 || 0.00180 [ YES ] 0.00180 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.520945 -2.019106 0.998439 H 1.819063 -1.927129 2.038936 C 0.169665 -2.036422 0.673486 H -0.594666 -1.967388 1.441036 C -0.210168 -2.048568 -0.668649 O -1.542427 -1.838105 -1.005387 C -1.980124 -0.566210 -0.649283 C 0.743310 -2.196047 -1.673975 H 0.422020 -2.251403 -2.709718 C 2.097638 -2.178645 -1.332178 H 2.844554 -2.221580 -2.122579 C 2.503854 -2.017992 -0.001336 C -3.151015 -0.450236 0.124499 O -3.767897 -1.616845 0.466622 C -4.948731 -1.536734 1.247074 H -5.740425 -0.980825 0.727051 H -4.759736 -1.065483 2.221145 H -5.273767 -2.567199 1.401959 C -3.573135 0.829149 0.498173 H -4.464260 0.954959 1.102789 C -2.840988 1.958924 0.118467 H -3.190095 2.939332 0.432731 C -1.684714 1.852906 -0.656743 C -0.962192 3.087831 -1.160333 H -0.974878 3.059615 -2.257000 C 0.526834 3.365873 -0.727172 H 0.547782 4.320247 -0.189713 H 1.137659 3.496343 -1.626202 C 1.230667 2.383659 0.201557 C 2.308844 1.572390 -0.318422 H 2.532727 1.587381 -1.378162 C 3.063662 0.780528 0.513838 O 2.851940 0.737308 1.824758 H 2.048081 1.328988 1.988673 C 4.174244 -0.118078 0.035759 H 5.113727 0.191622 0.512857 H 4.291121 0.020104 -1.043621 C 3.921040 -1.626486 0.350591


S94

S94

H 4.660339 -2.214496 -0.206723 H 4.102282 -1.801066 1.415649 O 0.911514 2.351962 1.410373 H -1.558786 3.962345 -0.883176 C -1.277087 0.567914 -1.039764 H -0.383058 0.433167 -1.641020 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.03479427 Predicted Change= -4.289358D-09 Zero-point correction (ZPE)= -1074.6737 0.36108 Internal Energy (U)= -1074.6540 0.38071 Enthalpy (H)= -1074.6531 0.38165 Gibbs Free Energy (G)= -1074.7214 0.31330 ------------------------------------------------------------------------------ Frequencies -- -137.4291 21.0074 56.4991

5.5.10 TSc→cb Supporting Information: Z-9-desmethylgarugamblin-c-pAnsa-CO-d-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.03467044 Predicted Change= -3.813767D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00139 || 0.00180 [ YES ] 0.00139 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.338755 -2.727812 -0.936122 H -1.955039 -3.029068 -1.780635 C 0.041221 -2.611765 -1.113249 H 0.503873 -2.799583 -2.077275 C 0.824069 -2.147785 -0.057626 O 2.143786 -1.774094 -0.289457 C 2.318091 -0.396871 -0.326804 C 0.261182 -1.944445 1.202686 H 0.894172 -1.615969 2.021187 C -1.118560 -2.056658 1.361300 H -1.564431 -1.823794 2.325187 C -1.947341 -2.377129 0.277878 C 3.594861 0.120243 -0.023254 O 4.567149 -0.796155 0.245937 C 5.863132 -0.314742 0.559141 H 5.855718 0.308675 1.463550 H 6.291945 0.262215 -0.271236 H 6.475213 -1.200881 0.736575 C 3.759303 1.508706 -0.008437 H 4.728703 1.934109 0.225963 C 2.681307 2.369726 -0.260945 H 2.840597 3.443800 -0.204269 C 1.420747 1.863216 -0.573839 C 0.191914 2.733032 -0.763045 H 0.498176 3.756652 -1.002503 C -0.745324 2.777168 0.497033 H -0.843368 3.803801 0.859554 H -0.285601 2.189204 1.301115 C -2.168997 2.259271 0.304922 C -2.393190 0.868218 -0.021670 H -1.551663 0.207271 -0.153453 C -3.666682 0.357906 -0.121692 O -4.738031 1.123562 0.063113 H -4.381826 2.049401 0.262318 C -4.025435 -1.066794 -0.495888 H -3.718531 -1.230167 -1.537182 H -5.118186 -1.125753 -0.475992 C -3.450296 -2.219536 0.376455 H -3.741268 -2.061441 1.421038 H -3.952695 -3.138732 0.047617 O -3.122932 3.052735 0.473634 H -0.378011 2.375626 -1.629524 C 1.279037 0.471422 -0.637337

H 0.320733 0.054022 -0.914895 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.03467044 Predicted Change= -3.813767D-09 Zero-point correction (ZPE)= -1074.6734 0.36122 Internal Energy (U)= -1074.6538 0.38078 Enthalpy (H)= -1074.6529 0.38172 Gibbs Free Energy (G)= -1074.7208 0.31386 ------------------------------------------------------------------------------ Frequencies -- -41.1976 30.5642 61.3230

5.5.11 Intab Supporting Information: Z-9-desmethylgarugamblin-a-mAnsa-CO-e-GS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.04022375 Predicted Change= -4.495398D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.01075 || 0.00180 [ NO ] 0.01075 || 0.00180 [ NO ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.373419 -2.147493 1.466131 H 1.719837 -2.120553 2.497243 C 0.005103 -2.113574 1.207694 H -0.718179 -2.053035 2.015015 C -0.435676 -2.045822 -0.113432 O -1.768637 -1.774370 -0.382407 C -2.144729 -0.453321 -0.190382 C 0.467895 -2.169560 -1.166682 H 0.100188 -2.150558 -2.187851 C 1.834842 -2.216269 -0.891124 H 2.535476 -2.240471 -1.722086 C 2.309817 -2.124351 0.424266 C -3.530162 -0.191409 -0.157754 O -4.349788 -1.269543 -0.323747 C -5.748426 -1.045215 -0.301244 H -6.062541 -0.363898 -1.103644 H -6.078638 -0.637737 0.664173 H -6.209888 -2.022248 -0.456610 C -3.951864 1.123079 0.051080 H -5.010839 1.351933 0.093181 C -3.022834 2.154843 0.232039 H -3.386574 3.163646 0.412235 C -1.650425 1.907965 0.186556 C -0.649032 3.037826 0.365019 H -0.368005 3.459477 -0.609115 C 0.663917 2.669187 1.099550 H 0.481067 1.939749 1.895523 H 1.051281 3.576793 1.583756 C 1.784751 2.195476 0.178014 C 2.587880 1.054562 0.549157 H 2.367086 0.522453 1.464253 C 3.538515 0.560956 -0.315373 O 3.819651 1.174333 -1.458891 H 3.203522 1.977213 -1.501129 C 4.365523 -0.693733 -0.131981 H 5.340729 -0.404296 0.284757 H 4.579712 -1.053315 -1.144408 C 3.769751 -1.838627 0.723550 H 4.398183 -2.724143 0.557012 H 3.868198 -1.596963 1.788254 O 1.985470 2.825755 -0.886472 H -1.143248 3.847269 0.914229 C -1.232609 0.588165 -0.039489 H -0.174872 0.363171 -0.086221 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.04022375 Predicted Change= -4.495398D-08


S95

S95

Zero-point correction (ZPE)= -1074.6790 0.36115 Internal Energy (U)= -1074.6587 0.38146 Enthalpy (H)= -1074.6578 0.38241 Gibbs Free Energy (G)= -1074.7282 0.31198 ------------------------------------------------------------------------------ Frequencies -- 19.3969 32.5049 59.3460

5.5.12 Intac Supporting Information: Z-9-desmethylgarugamblin-a-mAnsa-pAnsa-e-GS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.04022375 Predicted Change= -6.029430D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00812 || 0.00180 [ NO ] 0.00812 || 0.00180 [ NO ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.372865 -2.147613 1.466036 H 1.719041 -2.120739 2.497231 C 0.004624 -2.113652 1.207247 H -0.718883 -2.053120 2.014364 C -0.435832 -2.045809 -0.113990 O -1.768751 -1.774220 -0.383156 C -2.144747 -0.453164 -0.190948 C 0.467966 -2.169498 -1.167035 H 0.100524 -2.150407 -2.188299 C 1.834844 -2.216255 -0.891128 H 2.535706 -2.240387 -1.721901 C 2.309493 -2.124444 0.424387 C -3.530194 -0.191244 -0.157803 O -4.349853 -1.269356 -0.323749 C -5.748488 -1.045121 -0.300192 H -6.063226 -0.363673 -1.102238 H -6.078018 -0.637838 0.665539 H -6.210004 -2.022151 -0.455411 C -3.951825 1.123177 0.051456 H -5.010781 1.352031 0.094020 C -3.022713 2.154923 0.232282 H -3.386393 3.163679 0.412863 C -1.650344 1.908078 0.186190 C -0.648832 3.037828 0.364388 H -0.367443 3.458994 -0.609849 C 0.663957 2.669244 1.099378 H 0.480918 1.939820 1.895317 H 1.051144 3.576899 1.583607 C 1.784985 2.195489 0.178094 C 2.588069 1.054608 0.549454 H 2.367096 0.522523 1.464525 C 3.538874 0.560913 -0.314836 O 3.820025 1.174007 -1.458496 H 3.203996 1.976924 -1.500782 C 4.365564 -0.693991 -0.131396 H 5.340697 -0.404805 0.285704 H 4.579928 -1.053518 -1.143780 C 3.769380 -1.838846 0.723985 H 4.397722 -2.724445 0.557553 H 3.867649 -1.597177 1.788694 O 1.985817 2.825686 -0.886427 H -1.143009 3.847608 0.913131 C -1.232596 0.588295 -0.040276 H -0.174869 0.363344 -0.087418 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.04022375 Predicted Change= -6.029430D-08 Zero-point correction (ZPE)= -1074.6790 0.36115 Internal Energy (U)= -1074.6587 0.38146 Enthalpy (H)= -1074.6578 0.38241 Gibbs Free Energy (G)= -1074.7282 0.31198 ------------------------------------------------------------------------------

Frequencies -- 19.4045 32.4124 59.3292

5.5.13 Intbc Supporting Information: Z-9-desmethylgarugamblin-b-CO-c-GS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.04449342 Predicted Change= -1.240746D-08 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00145 || 0.00180 [ YES ] 0.00145 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.750688 -2.480350 -1.208518 H -2.293603 -2.690058 -2.128011 C -0.354876 -2.518517 -1.217000 H 0.198514 -2.741733 -2.124080 C 0.339060 -2.162136 -0.062248 O 1.711270 -1.947369 -0.116791 C 2.064059 -0.612362 -0.238325 C -0.341816 -1.916769 1.128839 H 0.222547 -1.675094 2.024120 C -1.733389 -1.887590 1.124323 H -2.265308 -1.619935 2.032769 C -2.454876 -2.094553 -0.060109 C 3.392820 -0.266693 0.089606 O 4.195163 -1.290426 0.498397 C 5.536066 -0.984668 0.839881 H 5.589545 -0.277397 1.678737 H 6.087087 -0.569717 -0.015000 H 5.991230 -1.931289 1.136973 C 3.780196 1.070468 -0.023017 H 4.794196 1.362565 0.225571 C 2.873927 2.048685 -0.452983 H 3.210158 3.079831 -0.532143 C 1.562613 1.712953 -0.786106 C 0.564570 2.744426 -1.277863 H 1.113676 3.598332 -1.692742 C -0.404105 3.310440 -0.209912 H -0.946438 4.155274 -0.662578 H 0.159709 3.714297 0.636481 C -1.473468 2.399387 0.385490 C -2.271543 1.526538 -0.448504 H -2.075532 1.452695 -1.510893 C -3.264002 0.749305 0.102193 O -3.562841 0.798541 1.395756 H -2.913806 1.466436 1.796361 C -4.082855 -0.253596 -0.667180 H -3.798853 -0.211244 -1.723396 H -5.142130 0.027011 -0.594267 C -3.915261 -1.709686 -0.130989 H -4.374544 -1.773226 0.860329 H -4.475318 -2.378303 -0.795590 O -1.682591 2.480759 1.617522 H -0.013479 2.327354 -2.112441 C 1.179791 0.368790 -0.675160 H 0.167006 0.087728 -0.933786 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.04449342 Predicted Change= -1.240746D-08 Zero-point correction (ZPE)= -1074.6832 0.36124 Internal Energy (U)= -1074.6630 0.38144 Enthalpy (H)= -1074.6621 0.38238 Gibbs Free Energy (G)= -1074.7318 0.31269 ------------------------------------------------------------------------------ Frequencies -- 21.1114 47.9069 69.7012


S96

S96

5.5.14 Intca Supporting Information: Z-9-desmethylgarugamblin-c-pAnsa-mAnsa-g-GS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.04449345 Predicted Change= -8.029932D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00092 || 0.00180 [ YES ] 0.00092 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.733311 -1.887638 1.124256 H 2.265063 -1.620052 2.032819 C 0.341737 -1.916911 1.128554 H -0.222771 -1.675374 2.023782 C -0.338931 -2.162192 -0.062661 O -1.711149 -1.947524 -0.117410 C -2.063957 -0.612500 -0.238682 C 0.355213 -2.518398 -1.217350 H -0.198032 -2.741560 -2.124531 C 1.751018 -2.480131 -1.208649 H 2.294097 -2.689689 -2.128079 C 2.454997 -2.094416 -0.060080 C -3.392614 -0.266824 0.089675 O -4.194868 -1.290571 0.498598 C -5.535720 -0.984839 0.840312 H -6.086844 -0.569751 -0.014436 H -5.589075 -0.277690 1.679279 H -5.990862 -1.931495 1.137327 C -3.779972 1.070359 -0.022682 H -4.793890 1.362468 0.226225 C -2.873797 2.048606 -0.452796 H -3.210053 3.079761 -0.531766 C -1.562593 1.712881 -0.786316 C -0.564598 2.744285 -1.278263 H 0.013558 2.327006 -2.112654 C 0.403996 3.310603 -0.210351 H -0.159922 3.714831 0.635790 H 0.946523 4.155166 -0.663278 C 1.473045 2.399512 0.385556 C 2.271538 1.526775 -0.448245 H 2.075945 1.453104 -1.510727 C 3.263809 0.749474 0.102604 O 3.562306 0.798420 1.396296 H 2.913206 1.466064 1.796886 C 4.082930 -0.253286 -0.666691 H 5.142161 0.027434 -0.593560 H 3.799139 -0.210844 -1.722963 C 3.915369 -1.709428 -0.130691 H 4.475559 -2.377945 -0.795282 H 4.374497 -1.773074 0.860691 O 1.681519 2.480706 1.617673 H -1.113664 3.598086 -1.693419 C -1.179785 0.368676 -0.675632 H -0.167071 0.087635 -0.934576 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.04449345 Predicted Change= -8.029932D-09 Zero-point correction (ZPE)= -1074.6832 0.36125 Internal Energy (U)= -1074.6630 0.38144 Enthalpy (H)= -1074.6621 0.38239 Gibbs Free Energy (G)= -1074.7317 0.31269 ------------------------------------------------------------------------------ Frequencies -- 21.1073 47.9131 69.7012

5.5.15 Intcb Supporting Information: Z-9-desmethylgarugamblin-c-pAnsa-CO-e-GS.log ------------------------------------------------------------------------------

Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.04449340 Predicted Change= -3.274844D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00527 || 0.00180 [ NO ] 0.00527 || 0.00180 [ NO ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.750298 -2.480265 -1.208515 H -2.292816 -2.690054 -2.128225 C -0.354486 -2.518326 -1.216408 H 0.199305 -2.741490 -2.123253 C 0.338955 -2.161921 -0.061361 O 1.711159 -1.947085 -0.115424 C 2.064032 -0.612167 -0.237496 C -0.342427 -1.916634 1.129450 H 0.221536 -1.674948 2.024981 C -1.734010 -1.887585 1.124355 H -2.266328 -1.620041 2.032597 C -2.454998 -2.094584 -0.060377 C 3.393081 -0.266686 0.089547 O 4.195413 -1.290490 0.498174 C 5.536673 -0.984985 0.838479 H 5.591022 -0.277491 1.677092 H 6.087098 -0.570412 -0.016970 H 5.991837 -1.931639 1.135466 C 3.780686 1.070334 -0.023719 H 4.794899 1.362304 0.224150 C 2.874357 2.048608 -0.453467 H 3.210779 3.079648 -0.533199 C 1.562749 1.713092 -0.785605 C 0.564756 2.744742 -1.277081 H 1.113955 3.598795 -1.691527 C -0.403997 3.310323 -0.209006 H -0.946054 4.155570 -0.661251 H 0.159748 3.713617 0.637708 C -1.473751 2.399315 0.385774 C -2.271431 1.526527 -0.448675 H -2.074767 1.452656 -1.510948 C -3.264107 0.749159 0.101419 O -3.563698 0.798264 1.394829 H -2.915037 1.466115 1.795916 C -4.082473 -0.253763 -0.668460 H -3.797559 -0.211644 -1.724427 H -5.141786 0.027009 -0.596521 C -3.915378 -1.709773 -0.131961 H -4.375109 -1.773064 0.859148 H -4.475165 -2.378470 -0.796718 O -1.683450 2.480639 1.617704 H -0.013185 2.328042 -2.111928 C 1.179665 0.369045 -0.673977 H 0.166645 0.088137 -0.931846 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.04449340 Predicted Change= -3.274844D-08 Zero-point correction (ZPE)= -1074.6832 0.36125 Internal Energy (U)= -1074.6630 0.38144 Enthalpy (H)= -1074.6621 0.38239 Gibbs Free Energy (G)= -1074.7317 0.31269 ------------------------------------------------------------------------------ Frequencies -- 21.1368 47.8978 69.7090

5.5.16 TSab→abc Supporting Information: Z-9-desmethylgarugamblin-a-mAnsa-CO-f-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity


S97

S97

#N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.03929874 Predicted Change= -5.181860D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00082 || 0.00180 [ YES ] 0.00082 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.428366 -2.030023 1.431181 H 1.730954 -2.005401 2.475847 C 0.073088 -2.009247 1.114816 H -0.684653 -1.959063 1.890540 C -0.313478 -1.962359 -0.224486 O -1.644930 -1.744731 -0.549449 C -2.102926 -0.464033 -0.277927 C 0.636780 -2.067086 -1.238517 H 0.311837 -2.056910 -2.274229 C 1.992147 -2.099628 -0.905436 H 2.730808 -2.114945 -1.702919 C 2.408658 -2.015811 0.430307 C -3.492429 -0.299344 -0.104952 O -4.253136 -1.425405 -0.226084 C -5.654116 -1.296410 -0.060025 H -6.089788 -0.617198 -0.805374 H -5.911989 -0.937110 0.945754 H -6.064942 -2.297897 -0.201198 C -3.975056 0.978332 0.187726 H -5.037211 1.134906 0.339168 C -3.100393 2.064660 0.316234 H -3.509065 3.040929 0.566038 C -1.725903 1.913097 0.129625 C -0.778290 3.095460 0.244905 H -0.535110 3.481763 -0.753053 C 0.559614 2.810154 0.963368 H 0.407802 2.189943 1.853769 H 0.976947 3.765206 1.316160 C 1.632066 2.193572 0.068526 C 2.594129 1.277007 0.632100 H 2.547798 1.025822 1.684850 C 3.493429 0.625750 -0.181739 O 3.564201 0.879898 -1.482832 H 2.860405 1.585434 -1.666146 C 4.471258 -0.441418 0.256310 H 5.129009 -0.021958 1.026895 H 5.098368 -0.648062 -0.614952 C 3.858011 -1.783066 0.800691 H 4.492785 -2.600672 0.437569 H 3.941589 -1.795885 1.892276 O 1.655310 2.506020 -1.145357 H -1.295248 3.903452 0.774966 C -1.251284 0.631711 -0.183880 H -0.193886 0.473478 -0.349155 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.03929874 Predicted Change= -5.181860D-09 Zero-point correction (ZPE)= -1074.6784 0.36079 Internal Energy (U)= -1074.6588 0.38046 Enthalpy (H)= -1074.6578 0.38140 Gibbs Free Energy (G)= -1074.7266 0.31266 ------------------------------------------------------------------------------ Frequencies -- -82.0337 17.7362 47.1296

5.5.17 TSac→acb Supporting Information: Z-9-desmethylgarugamblin-a-mAnsa-pAnsa-f-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1

------------------------------------------------------------------------------ SCF Energy= -1075.03929876 Predicted Change= 2.991154D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00086 || 0.00180 [ YES ] 0.00086 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.427942 -2.030265 1.431155 H 1.730460 -2.005701 2.475843 C 0.072691 -2.009396 1.114684 H -0.685110 -1.959167 1.890346 C -0.313773 -1.962446 -0.224650 O -1.645182 -1.744658 -0.549689 C -2.103046 -0.463944 -0.278049 C 0.636545 -2.067214 -1.238612 H 0.311676 -2.056964 -2.274347 C 1.991889 -2.099823 -0.905426 H 2.730606 -2.115160 -1.702858 C 2.408307 -2.016062 0.430349 C -3.492528 -0.299106 -0.105027 O -4.253374 -1.425068 -0.226213 C -5.654324 -1.295919 -0.060013 H -6.089988 -0.616614 -0.805281 H -5.912046 -0.936641 0.945811 H -6.065283 -2.297349 -0.201202 C -3.974987 0.978609 0.187753 H -5.037116 1.135305 0.339255 C -3.100189 2.064831 0.316306 H -3.508735 3.041129 0.566199 C -1.725729 1.913118 0.129613 C -0.777946 3.095341 0.244825 H -0.534532 3.481446 -0.753156 C 0.559825 2.809937 0.963523 H 0.407852 2.189527 1.853753 H 0.977048 3.764934 1.316588 C 1.632483 2.193609 0.068741 C 2.594192 1.276578 0.632156 H 2.547455 1.024877 1.684763 C 3.493610 0.625531 -0.181722 O 3.564849 0.880304 -1.482667 H 2.861270 1.586090 -1.665857 C 4.471139 -0.442006 0.256132 H 5.129338 -0.022690 1.026414 H 5.097874 -0.648980 -0.615326 C 3.857649 -1.783360 0.800831 H 4.492363 -2.601173 0.438061 H 3.941086 -1.795847 1.892432 O 1.656181 2.506660 -1.144978 H -1.294874 3.903507 0.774647 C -1.251287 0.631696 -0.183976 H -0.193914 0.473331 -0.349281 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.03929876 Predicted Change= 2.991154D-10 Zero-point correction (ZPE)= -1074.6784 0.36080 Internal Energy (U)= -1074.6588 0.38046 Enthalpy (H)= -1074.6578 0.38140 Gibbs Free Energy (G)= -1074.7266 0.31266 ------------------------------------------------------------------------------ Frequencies -- -81.9821 17.7727 47.1158

5.5.18 TSbc→bca Supporting Information: Z-9-desmethylgarugamblin-b-CO-mAnsa-d-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.03479431 Predicted Change= -1.023868D-09 ============================================================================== Optimization completed. {Found 2 times}


S98

S98

Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00088 || 0.00180 [ YES ] 0.00088 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -2.097744 -2.178216 -1.332323 H -2.844852 -2.220869 -2.122558 C -0.743506 -2.195581 -1.674447 H -0.422467 -2.250644 -2.710283 C 0.210217 -2.048467 -0.669307 O 1.542395 -1.837924 -1.006342 C 1.980062 -0.566120 -0.649828 C -0.169283 -2.036722 0.672931 H 0.595247 -1.967975 1.440308 C -1.520490 -2.019423 0.998211 H -1.818367 -1.927742 2.038804 C -2.503629 -2.017957 -0.001337 C 3.150582 -0.450311 0.124533 O 3.767246 -1.616998 0.466786 C 4.947701 -1.537061 1.247833 H 4.758259 -1.065915 2.221868 H 5.739690 -0.981145 0.728267 H 5.272589 -2.567567 1.402753 C 3.572565 0.829002 0.498619 H 4.463424 0.954690 1.103652 C 2.840589 1.958857 0.118813 H 3.189550 2.939201 0.433441 C 1.684658 1.853003 -0.656930 C 0.962190 3.087997 -1.160435 H 1.558822 3.962472 -0.883253 C -0.526843 3.365999 -0.727167 H -1.137788 3.496450 -1.626115 H -0.547803 4.320367 -0.189695 C -1.230453 2.383705 0.201639 C -2.308771 1.572488 -0.318139 H -2.532971 1.587626 -1.377810 C -3.063314 0.780480 0.514228 O -2.851179 0.737055 1.825076 H -2.047305 1.328743 1.988847 C -4.174022 -0.118094 0.036372 H -4.291196 0.020125 -1.042971 H -5.113372 0.191624 0.513722 C -3.920722 -1.626514 0.351015 H -4.101659 -1.801169 1.416114 H -4.660170 -2.214514 -0.206116 O -0.910957 2.351870 1.410359 H 0.974823 3.059840 -2.257102 C 1.277220 0.568087 -1.040413 H 0.383465 0.433456 -1.642106 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.03479431 Predicted Change= -1.023868D-09 Zero-point correction (ZPE)= -1074.6737 0.36108 Internal Energy (U)= -1074.6540 0.38071 Enthalpy (H)= -1074.6531 0.38165 Gibbs Free Energy (G)= -1074.7214 0.31330 ------------------------------------------------------------------------------ Frequencies -- -137.3449 21.0018 56.5213

5.5.19 TSca→cab Supporting Information: Z-9-desmethylgarugamblin-c-pAnsa-mAnsa-Co-h-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.03467044 Predicted Change= 6.793370D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00121 || 0.00180 [ YES ] 0.00121 || 0.00180 [ YES ] ------------------------------------------------------------------------------

Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.118862 -2.056826 1.361284 H 1.564892 -1.824116 2.325134 C -0.260914 -1.944649 1.202936 H -0.893774 -1.616336 2.021603 C -0.824014 -2.147801 -0.057310 O -2.143784 -1.774116 -0.288838 C -2.318089 -0.396901 -0.326386 C -0.041330 -2.611535 -1.113164 H -0.504146 -2.799175 -2.077145 C 1.338680 -2.727555 -0.936302 H 1.954839 -3.028614 -1.780978 C 1.947462 -2.377078 0.277661 C -3.594955 0.120211 -0.023213 O -4.567272 -0.796192 0.245855 C -5.863386 -0.314800 0.558545 H -6.291927 0.262049 -0.272047 H -5.856335 0.308709 1.462895 H -6.475492 -1.200946 0.735854 C -3.759451 1.508665 -0.008631 H -4.728917 1.934065 0.225500 C -2.681445 2.369695 -0.261076 H -2.840803 3.443772 -0.204645 C -1.420796 1.863190 -0.573608 C -0.192012 2.733058 -0.762899 H 0.377831 2.375755 -1.629478 C 0.745375 2.777228 0.497064 H 0.285700 2.189389 1.301268 H 0.843514 3.803888 0.859487 C 2.169020 2.259250 0.304938 C 2.393221 0.868251 -0.021861 H 1.551711 0.207336 -0.153886 C 3.666716 0.357944 -0.121869 O 4.738065 1.123540 0.063169 H 4.381865 2.049355 0.262499 C 4.025477 -1.066698 -0.496260 H 5.118232 -1.125642 -0.476455 H 3.718497 -1.229959 -1.537549 C 3.450437 -2.219539 0.376014 H 3.952752 -3.138710 0.046977 H 3.741588 -2.061603 1.420573 O 3.122969 3.052658 0.473852 H -0.498372 3.756670 -1.002265 C -1.278999 0.471390 -0.636792 H -0.320624 0.053993 -0.914070 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.03467044 Predicted Change= 6.793370D-10 Zero-point correction (ZPE)= -1074.6734 0.36122 Internal Energy (U)= -1074.6538 0.38078 Enthalpy (H)= -1074.6529 0.38172 Gibbs Free Energy (G)= -1074.7208 0.31386 ------------------------------------------------------------------------------ Frequencies -- -41.2674 30.5453 61.3271

5.5.20 TScb→cba Supporting Information: Z-9-desmethylgarugamblin-c-pAnsa-CO-mAnsa-f-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.03479431 Predicted Change= -9.759679D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00086 || 0.00180 [ YES ] 0.00086 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -2.097742 -2.178221 -1.332321


S99

S99

H -2.844848 -2.220877 -2.122557 C -0.743503 -2.195587 -1.674441 H -0.422461 -2.250654 -2.710276 C 0.210218 -2.048470 -0.669300 O 1.542396 -1.837928 -1.006332 C 1.980062 -0.566122 -0.649822 C -0.169286 -2.036720 0.672937 H 0.595241 -1.967970 1.440317 C -1.520494 -2.019420 0.998214 H -1.818374 -1.927736 2.038806 C -2.503630 -2.017958 -0.001337 C 3.150586 -0.450309 0.124533 O 3.767253 -1.616995 0.466786 C 4.947712 -1.537055 1.247826 H 4.758273 -1.065907 2.221861 H 5.739697 -0.981139 0.728256 H 5.272602 -2.567560 1.402747 C 3.572569 0.829005 0.498614 H 4.463431 0.954695 1.103642 C 2.840591 1.958858 0.118807 H 3.189554 2.939203 0.433430 C 1.684657 1.853001 -0.656930 C 0.962187 3.087994 -1.160437 H 1.558821 3.962469 -0.883259 C -0.526843 3.366000 -0.727164 H -1.137788 3.496454 -1.626111 H -0.547798 4.320367 -0.189691 C -1.230455 2.383707 0.201640 C -2.308772 1.572489 -0.318142 H -2.532968 1.587625 -1.377813 C -3.063317 0.780481 0.514223 O -2.851187 0.737057 1.825072 H -2.047313 1.328745 1.988846 C -4.174022 -0.118095 0.036364 H -4.291192 0.020123 -1.042980 H -5.113375 0.191624 0.513710 C -3.920724 -1.626514 0.351010 H -4.101664 -1.801167 1.416110 H -4.660170 -2.214515 -0.206121 O -0.910964 2.351872 1.410361 H 0.974817 3.059834 -2.257103 C 1.277218 0.568084 -1.040408 H 0.383460 0.433451 -1.642096 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.03479431 Predicted Change= -9.759679D-10 Zero-point correction (ZPE)= -1074.6737 0.36108 Internal Energy (U)= -1074.6540 0.38071 Enthalpy (H)= -1074.6531 0.38165 Gibbs Free Energy (G)= -1074.7214 0.31330 ------------------------------------------------------------------------------ Frequencies -- -137.3461 21.0017 56.5210

5.5.21 ent- C9-Z-9’-

Desmethylgarugamblin I Supporting Information: Z-9-desmethylgarugamblin-a-mAnsa-CO-g-GS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.04829692 Predicted Change= -2.471234D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00063 || 0.00180 [ YES ] 0.00063 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.719124 -2.314592 -1.142780 H -2.211477 -2.481493 -2.098805 C -0.326690 -2.268287 -1.093393 H 0.275071 -2.390769 -1.988659

C 0.304950 -2.000027 0.120798 O 1.678862 -1.812075 0.146109 C 2.116088 -0.501042 0.070351 C -0.436253 -1.883078 1.294758 H 0.077205 -1.702601 2.234036 C -1.828560 -1.916549 1.227686 H -2.409735 -1.753865 2.131457 C -2.490657 -2.080703 0.004336 C 3.515205 -0.315658 0.028173 O 4.271058 -1.450951 0.070257 C 5.679792 -1.307193 0.036895 H 6.048332 -0.726068 0.893247 H 6.016827 -0.828036 -0.892556 H 6.084538 -2.319793 0.087341 C 4.011221 0.985159 -0.059199 H 5.081066 1.155922 -0.101970 C 3.141767 2.082658 -0.101402 H 3.561167 3.083398 -0.171646 C 1.759315 1.910498 -0.049767 C 0.825029 3.108845 -0.046070 H 0.533016 3.358104 0.982692 C -0.476253 2.950684 -0.864845 H -0.285841 2.430499 -1.809661 H -0.843694 3.954058 -1.125160 C -1.622295 2.282896 -0.110975 C -2.465775 1.336488 -0.802182 H -2.256120 1.083210 -1.833944 C -3.466982 0.668322 -0.139008 O -3.758789 0.912843 1.134026 H -3.103367 1.620716 1.432534 C -4.275573 -0.442260 -0.751583 H -4.057360 -0.485956 -1.822975 H -5.343268 -0.216088 -0.636266 C -3.978868 -1.826406 -0.095279 H -4.426946 -1.846543 0.902906 H -4.482113 -2.595825 -0.693729 O -1.818038 2.580706 1.089047 H 1.375480 3.976013 -0.428039 C 1.264657 0.598797 0.032447 H 0.196500 0.429625 0.069912 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.04829692 Predicted Change= -2.471234D-09 Zero-point correction (ZPE)= -1074.6869 0.36137 Internal Energy (U)= -1074.6666 0.38168 Enthalpy (H)= -1074.6656 0.38263 Gibbs Free Energy (G)= -1074.7361 0.31210 ------------------------------------------------------------------------------ Frequencies -- 12.9852 45.9062 63.0150

5.6 C9-E-9’-Desmethylgarugamblin I

5.6.1 C9-E-9’-Desmethylgarugamblin I Supporting Information: E-9-desmethylgarugamblin-a-mAnsa-a-GS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.02921951 Predicted Change= -4.989607D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00418 || 0.00180 [ NO ] 0.00418 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.654493 -2.218108 -1.379602 H -2.212846 -2.317924 -2.307681 C -0.260432 -2.254065 -1.416630 H 0.276122 -2.370401 -2.353129 C 0.454220 -2.032829 -0.241758 O 1.828761 -1.831255 -0.295637 C 2.196792 -0.494508 -0.239931


S100

S100

C -0.207635 -1.916371 0.980386 H 0.373251 -1.779564 1.887366 C -1.600013 -1.889082 1.002512 H -2.118154 -1.743552 1.947537 C -2.341811 -1.971852 -0.184107 C 3.511448 -0.202282 0.181457 O 4.301155 -1.275214 0.478313 C 5.632988 -1.021539 0.887105 H 5.668405 -0.438925 1.818113 H 6.201106 -0.490348 0.111238 H 6.084796 -2.000593 1.058002 C 3.896202 1.137041 0.271747 H 4.897859 1.392055 0.599671 C 2.995716 2.166769 -0.036605 H 3.323026 3.199050 0.063457 C 1.700818 1.883765 -0.468292 C 0.696551 2.975304 -0.793103 H 1.193148 3.948949 -0.712998 C -0.551298 2.984762 0.116539 H -1.022078 3.979994 0.076000 H -0.267146 2.828408 1.164377 C -1.654999 1.988972 -0.280302 C -2.592752 1.636552 0.796293 H -2.421881 2.138532 1.749619 C -3.607919 0.734141 0.745005 O -4.370878 0.477973 1.841600 H -4.062273 1.022908 2.585569 C -4.051384 -0.110100 -0.415797 H -3.530037 0.227754 -1.311556 H -5.128909 0.057693 -0.546076 C -3.815443 -1.637245 -0.196914 H -4.298495 -1.946137 0.736500 H -4.321038 -2.165781 -1.013388 O -1.730783 1.568362 -1.432645 H 0.351184 2.874873 -1.829022 C 1.328484 0.535843 -0.580780 H 0.337691 0.293063 -0.939996 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.02921951 Predicted Change= -4.989607D-08 Zero-point correction (ZPE)= -1074.6681 0.36108 Internal Energy (U)= -1074.6474 0.38172 Enthalpy (H)= -1074.6465 0.38266 Gibbs Free Energy (G)= -1074.7172 0.31194 ------------------------------------------------------------------------------ Frequencies -- 23.7034 39.0264 65.4134

5.6.2 TSa Supporting Information: E-9-desmethylgarugamblin-a-mAnsa-b-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.01119153 Predicted Change= -2.354017D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00068 || 0.00180 [ YES ] 0.00068 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.899537 -1.996308 -1.445955 H -2.658473 -1.915153 -2.220286 C -0.552994 -1.955480 -1.808657 H -0.251650 -1.843800 -2.845549 C 0.413837 -1.931688 -0.807302 O 1.729913 -1.602458 -1.125184 C 2.068962 -0.351537 -0.618696 C 0.059764 -2.120258 0.528977 H 0.838527 -2.147303 1.284987 C -1.286859 -2.162779 0.874924 H -1.570210 -2.227700 1.922936 C -2.283864 -2.021645 -0.099992

C 3.232420 -0.243046 0.164732 O 3.960292 -1.384087 0.333221 C 5.151300 -1.302836 1.096675 H 4.949609 -1.006162 2.135291 H 5.867811 -0.596949 0.655440 H 5.580938 -2.306278 1.086470 C 3.531592 0.999057 0.733524 H 4.410213 1.117421 1.357848 C 2.682050 2.091089 0.536854 H 2.932614 3.037772 1.010449 C 1.535263 1.998295 -0.259790 C 0.724841 3.257955 -0.529735 H 0.973743 3.973335 0.261780 C -0.841547 3.241236 -0.689064 H -1.089037 3.599085 -1.691452 H -1.252624 3.971487 0.019696 C -1.671834 1.954522 -0.541793 C -2.008529 1.528017 0.823092 H -1.458305 2.023281 1.624338 C -2.955677 0.619480 1.180419 O -3.172285 0.308799 2.486519 H -2.528118 0.781181 3.041150 C -3.908112 -0.132013 0.290761 H -3.794428 0.243047 -0.725979 H -4.926150 0.084609 0.642657 C -3.696153 -1.677299 0.309626 H -3.912756 -2.061344 1.312212 H -4.431003 -2.117517 -0.375006 O -2.080763 1.394108 -1.557713 H 1.118852 3.709350 -1.450045 C 1.258519 0.758597 -0.849715 H 0.382540 0.630597 -1.475000 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.01119153 Predicted Change= -2.354017D-09 Zero-point correction (ZPE)= -1074.6503 0.36083 Internal Energy (U)= -1074.6303 0.38087 Enthalpy (H)= -1074.6293 0.38181 Gibbs Free Energy (G)= -1074.6988 0.31235 ------------------------------------------------------------------------------ Frequencies -- -166.0231 21.3688 41.5423

5.6.3 TSb Supporting Information: E-9-desmethylgarugamblin-b-CO-b-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.00191240 Predicted Change= -1.051170D-08 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00145 || 0.00180 [ YES ] 0.00145 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.100756 -2.646990 -1.245104 H -1.661513 -2.916730 -2.137514 C 0.293152 -2.582320 -1.313295 H 0.820822 -2.768334 -2.243806 C 1.004728 -2.147753 -0.198078 O 2.335546 -1.753525 -0.336543 C 2.452334 -0.366257 -0.335242 C 0.351020 -1.942203 1.018862 H 0.929219 -1.638777 1.886272 C -1.040198 -2.008577 1.071479 H -1.550803 -1.783221 2.004884 C -1.792782 -2.284727 -0.079911 C 3.650485 0.222387 0.120053 O 4.659997 -0.634533 0.445986 C 5.873811 -0.077535 0.920071 H 5.723507 0.490730 1.848174 H 6.338727 0.576878 0.170400


S101

S101

H 6.533394 -0.924421 1.118168 C 3.700206 1.616699 0.226612 H 4.604805 2.095945 0.584147 C 2.579906 2.412124 -0.064936 H 2.639542 3.486031 0.094460 C 1.402474 1.833894 -0.533552 C 0.087782 2.566743 -0.743304 H 0.200077 3.639895 -0.557022 C -0.998504 1.975859 0.182024 H -0.816046 2.278430 1.225239 H -0.935414 0.882148 0.214927 C -2.440112 2.334356 -0.130817 C -3.480793 1.620836 0.700272 H -3.926119 2.256755 1.468285 C -3.946989 0.365994 0.565895 O -4.899392 -0.148906 1.410654 H -5.090898 0.500765 2.106298 C -3.674815 -0.613611 -0.549239 H -2.921294 -0.205376 -1.229094 H -4.611305 -0.668175 -1.121119 C -3.289379 -2.067760 -0.117808 H -3.748807 -2.284617 0.851432 H -3.736623 -2.760202 -0.839655 O -2.745413 3.205506 -0.925585 H -0.246949 2.471188 -1.784347 C 1.394108 0.446254 -0.714307 H 0.495695 -0.021734 -1.094286 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.00191240 Predicted Change= -1.051170D-08 Zero-point correction (ZPE)= -1074.6422 0.35969 Internal Energy (U)= -1074.6220 0.37989 Enthalpy (H)= -1074.6210 0.38083 Gibbs Free Energy (G)= -1074.6905 0.31137 ------------------------------------------------------------------------------ Frequencies -- -64.2318 30.7652 42.8733

5.6.4 TSc Supporting Information: E-9-desmethylgarugamblin-c-pAnsa-CO-mAnsa-b2-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,modredundant) geom=connectivity Modredundant Input: D 32 34 37 12 F # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=allcheck guess=read #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1074.98761322 Predicted Change= -1.301992D-08 ============================================================================== Optimization completed. {Found 3 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00003 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00126 || 0.00180 [ YES ] 0.00126 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -0.687758 -2.700114 -0.998600 H -0.937424 -2.779182 -2.055383 C 0.624992 -2.413238 -0.631863 H 1.405433 -2.295427 -1.377526 C 0.908484 -2.118698 0.704146 O 2.096077 -1.474953 1.034891 C 2.143822 -0.158044 0.570205 C -0.040528 -2.372713 1.692508 H 0.216751 -2.214610 2.735393 C -1.354023 -2.656497 1.308708 H -2.128563 -2.684717 2.072650 C -1.718617 -2.690420 -0.044520 C 3.231633 0.206358 -0.247181 O 4.128067 -0.780253 -0.537392 C 5.258092 -0.439260 -1.321799 H 5.868126 0.334784 -0.837147 H 4.969275 -0.092534 -2.323629 H 5.844476 -1.355441 -1.413729

C 3.305831 1.523990 -0.708526 H 4.131677 1.837762 -1.337120 C 2.312835 2.449551 -0.373210 H 2.403500 3.468013 -0.744680 C 1.225164 2.103108 0.433911 C 0.190222 3.155777 0.817210 H -0.069661 3.047366 1.874950 C -1.130227 3.164264 0.008629 H -0.939329 3.040853 -1.065333 H -1.618311 4.146131 0.113072 C -2.132037 2.097563 0.462049 C -3.288289 1.806734 -0.429117 H -3.765033 2.651572 -0.927166 C -3.640959 0.538185 -0.764685 O -4.660853 0.226598 -1.600284 C -2.744180 -0.610967 -0.393968 H -2.399509 -0.404837 0.616097 H -1.858012 -0.477524 -1.027187 C -3.076662 -2.127540 -0.455531 H -3.875042 -2.395522 0.245391 H -3.379548 -2.441779 -1.459993 O -1.942604 1.497188 1.514641 H 0.655753 4.141619 0.702453 C 1.165817 0.778043 0.904437 H 0.341317 0.472539 1.539339 H -5.153039 1.035794 -1.822117 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1074.98761322 Predicted Change= -1.301992D-08 Zero-point correction (ZPE)= -1074.6277 0.35987 Internal Energy (U)= -1074.6077 0.37990 Enthalpy (H)= -1074.6067 0.38085 Gibbs Free Energy (G)= -1074.6759 0.31161 ------------------------------------------------------------------------------ Frequencies -- -129.1975 18.9119 50.9922

5.6.5 Inta Supporting Information: E-9-desmethylgarugamblin-a-mAnsa-c-GS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.02543796 Predicted Change= -8.954361D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00165 || 0.00180 [ YES ] 0.00165 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.478006 -1.911860 1.338055 H 1.870798 -1.741828 2.337088 C 0.101824 -1.950747 1.148098 H -0.583647 -1.804766 1.976827 C -0.405509 -2.068966 -0.146344 O -1.761545 -1.846643 -0.365992 C -2.111762 -0.506744 -0.323580 C 0.444383 -2.288607 -1.226085 H 0.025131 -2.406064 -2.220795 C 1.826226 -2.242229 -1.020237 H 2.495837 -2.335048 -1.872160 C 2.358499 -1.986565 0.248732 C -3.469880 -0.200136 -0.089763 O -4.307260 -1.265640 0.062148 C -5.677852 -1.000704 0.304302 H -6.135904 -0.444717 -0.525087 H -5.823708 -0.438068 1.236535 H -6.159047 -1.976495 0.393183 C -3.847276 1.142696 -0.024065 H -4.882553 1.405757 0.161546 C -2.900775 2.164447 -0.181422 H -3.226890 3.199652 -0.114435 C -1.560929 1.868494 -0.425507 C -0.514796 2.950456 -0.613679


S102

S102

H 0.015872 2.788101 -1.562053 C 0.517577 3.093730 0.537287 H -0.003505 3.214345 1.491290 H 1.091956 4.015020 0.354524 C 1.542801 1.967898 0.746207 C 2.416745 1.653592 -0.398274 H 2.215139 2.208678 -1.315402 C 3.449047 0.768661 -0.429935 O 4.171973 0.573760 -1.564889 H 3.805521 1.120941 -2.280378 C 3.975717 -0.089071 0.686671 H 3.463405 0.196336 1.605376 H 5.046076 0.133440 0.794743 C 3.813497 -1.616837 0.427215 H 4.392764 -1.900650 -0.457561 H 4.252709 -2.141618 1.284769 O 1.627830 1.429106 1.846644 H -1.020970 3.917727 -0.717535 C -1.190537 0.519034 -0.505801 H -0.156998 0.265341 -0.705010 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.02543796 Predicted Change= -8.954361D-09 Zero-point correction (ZPE)= -1074.6642 0.36118 Internal Energy (U)= -1074.6436 0.38177 Enthalpy (H)= -1074.6427 0.38271 Gibbs Free Energy (G)= -1074.7130 0.31235 ------------------------------------------------------------------------------ Frequencies -- 26.4905 47.2491 69.7020

5.6.6 Intb Supporting Information: E-9-desmethylgarugamblin-b-CO-c-GS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.01194626 Predicted Change= -3.775510D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00137 || 0.00180 [ YES ] 0.00137 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.482495 -2.548336 1.281000 H 1.985766 -2.781587 2.216985 C 0.090015 -2.640066 1.214297 H -0.498485 -2.914805 2.084431 C -0.558058 -2.228227 0.051904 O -1.922242 -1.957225 0.078938 C -2.175258 -0.597516 0.249597 C 0.174642 -1.916819 -1.094188 H -0.353139 -1.637696 -2.000845 C 1.562552 -1.843622 -1.017996 H 2.129899 -1.533147 -1.891306 C 2.229295 -2.069042 0.196325 C -3.419929 -0.093683 -0.174162 O -4.298053 -1.002137 -0.689792 C -5.556946 -0.526693 -1.132654 H -5.451979 0.199843 -1.949987 H -6.126739 -0.065301 -0.314573 H -6.095730 -1.403497 -1.497006 C -3.649048 1.281279 -0.053855 H -4.590971 1.701404 -0.388681 C -2.667303 2.139285 0.459133 H -2.870899 3.206206 0.502910 C -1.440150 1.642990 0.899358 C -0.361457 2.538070 1.493514 H -0.506385 3.560292 1.132814 C 1.090936 2.116019 1.186512 H 1.273231 1.080894 1.485149 H 1.774467 2.723712 1.798752 C 1.485638 2.349590 -0.272703 C 2.631298 1.693854 -0.939719

H 2.731053 2.116186 -1.941928 C 3.535828 0.731480 -0.627111 O 4.472237 0.371490 -1.557345 H 4.338624 0.896521 -2.364350 C 3.765996 -0.088497 0.615338 H 3.085130 0.210462 1.412828 H 4.786714 0.135519 0.953713 C 3.663832 -1.630414 0.378057 H 4.279759 -1.891160 -0.488321 H 4.103042 -2.128327 1.249887 O 0.856644 3.171443 -0.933031 H -0.474143 2.567278 2.587003 C -1.232858 0.264170 0.801177 H -0.297019 -0.154294 1.139420 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.01194626 Predicted Change= -3.775510D-10 Zero-point correction (ZPE)= -1074.6508 0.36112 Internal Energy (U)= -1074.6301 0.38175 Enthalpy (H)= -1074.6292 0.38269 Gibbs Free Energy (G)= -1074.7009 0.31100 ------------------------------------------------------------------------------ Frequencies -- 8.5812 38.0047 49.4744

5.6.7 Intc Supporting Information: E-9-desmethylgarugamblin-c-pAnsa-CO-mAnsa-e-GS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # opt=maxcycle=250 freq=noraman b3lyp/6-31g(d) geom=connectivity gfinput gfprint scf=(direct,tight,maxcycle=300,xqc) #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.00010543 Predicted Change= -2.071333D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00003 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00273 || 0.00180 [ NO ] 0.00273 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.074881 -2.348049 -0.996221 H -1.506659 -2.411203 -1.992994 C 0.309309 -2.287304 -0.868470 H 0.955825 -2.279699 -1.740790 C 0.868477 -2.111572 0.397622 O 2.196272 -1.699601 0.496840 C 2.339158 -0.325655 0.310578 C 0.069266 -2.198754 1.534253 H 0.523161 -2.098142 2.515441 C -1.320531 -2.228300 1.386701 H -1.945218 -2.151020 2.272786 C -1.913339 -2.199563 0.121218 C 3.564407 0.148453 -0.202276 O 4.519173 -0.792173 -0.460414 C 3.704153 1.523355 -0.416170 H 4.632297 1.916403 -0.815999 C 2.655533 2.410707 -0.133285 H 2.803961 3.472722 -0.316558 C 1.445992 1.949018 0.387160 C 0.312451 2.895331 0.764064 H 0.065390 2.756110 1.824442 C -1.008047 2.804945 -0.045411 H -0.793226 2.672717 -1.116444 H -1.545116 3.762189 0.021712 C -1.980720 1.693166 0.352162 C -3.375686 1.773434 -0.135389 H -3.869028 2.744685 -0.079544 C -4.079695 0.702562 -0.579833 O -5.418505 0.775839 -0.826579 C -3.519647 -0.615707 -1.062896 H -2.538125 -0.408041 -1.491109 H -4.170405 -0.910357 -1.893308 C -3.374592 -1.826267 -0.069274 H -3.820727 -1.582757 0.899420 H -3.947025 -2.670055 -0.474774


S103

S103

O -1.634502 0.754027 1.059250 H 0.681659 3.923272 0.666651 C 1.321010 0.570481 0.609392 H 0.389696 0.206426 1.014553 H -5.760904 1.618879 -0.484332 C 5.765497 -0.348343 -0.965354 H 6.266355 0.335152 -0.266118 H 6.374364 -1.245998 -1.089933 H 5.655543 0.152362 -1.937319 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.00010543 Predicted Change= -2.071333D-08 Zero-point correction (ZPE)= -1074.6400 0.36004 Internal Energy (U)= -1074.6190 0.38101 Enthalpy (H)= -1074.6181 0.38196 Gibbs Free Energy (G)= -1074.6899 0.31016 ------------------------------------------------------------------------------ Frequencies -- 21.4919 41.8493 47.9302

5.6.8 TSa→ab Supporting Information: E-9-desmethylgarugamblin-a-mAnsa-CO-c-scanIn-switchAtoms-TS1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk UB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4(3) C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 3 ------------------------------------------------------------------------------ SCF Energy= -1074.89656839 Predicted Change= -1.827228D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00005 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00151 || 0.00180 [ YES ] 0.00151 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.269299 -1.998861 -1.544190 H -1.674681 -1.838180 -2.540991 C 0.110268 -1.967650 -1.355699 H 0.785962 -1.767448 -2.181567 C 0.626776 -2.090562 -0.064357 O 1.962625 -1.787217 0.174515 C 2.222335 -0.424124 0.192259 C -0.210211 -2.393960 1.005355 H 0.216331 -2.517429 1.996182 C -1.591199 -2.427137 0.800906 H -2.252143 -2.588800 1.648042 C -2.143063 -2.156312 -0.458105 C 3.572947 -0.017256 0.128507 O 4.500048 -1.017435 0.088187 C 5.866107 -0.649597 0.014183 H 6.175023 -0.060734 0.888635 H 6.082846 -0.076843 -0.897920 H 6.426795 -1.586020 -0.006187 C 3.852681 1.350772 0.097085 H 4.880918 1.689806 0.037348 C 2.821316 2.302534 0.109570 H 3.076678 3.357745 0.050175 C 1.488417 1.907087 0.187456 C 0.318117 2.873429 0.158005 H -0.171285 2.886089 1.141120 C -0.745792 2.508393 -0.946366 H -0.387775 1.626563 -1.489449 H -0.801735 3.319216 -1.682009 C -2.158896 2.230721 -0.486612 C -2.565729 1.415047 0.683924 H -2.304809 1.794047 1.681991 C -3.412187 0.348122 0.639025 O -3.852143 -0.252402 1.775674 H -3.510187 0.235517 2.545332 C -3.924637 -0.345226 -0.590395 H -3.482355 0.148112 -1.460254 H -5.013122 -0.207129 -0.644734 C -3.621402 -1.875143 -0.610763 H -4.186193 -2.360708 0.191251 H -4.000167 -2.272091 -1.560342

O -3.042444 3.229325 -0.453553 H 0.685776 3.892526 -0.005063 C 1.217301 0.532605 0.254617 H 0.186338 0.210302 0.323439 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1074.89656839 Predicted Change= -1.827228D-09 Zero-point correction (ZPE)= -1074.5391 0.35741 Internal Energy (U)= -1074.5187 0.37784 Enthalpy (H)= -1074.5177 0.37878 Gibbs Free Energy (G)= -1074.5885 0.30800 ------------------------------------------------------------------------------ Frequencies -- -41.6377 34.6334 45.9584

5.6.9 TSa→acb Supporting Information: E-9-desmethylgarugamblin-a-mAnsa-pAnsa-c-scanIn-switchAtoms-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk UB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4(3) C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 3 ------------------------------------------------------------------------------ SCF Energy= -1074.88527695 Predicted Change= -8.481582D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00075 || 0.00180 [ YES ] 0.00075 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.744186 -1.748397 1.565518 H 1.162077 -1.391161 2.506453 C -0.600951 -1.846920 1.415919 H -1.278431 -1.577500 2.223318 C -1.164799 -2.375652 0.154915 O -2.146000 -1.643179 -0.517723 C -2.209403 -0.270422 -0.360035 C -0.218347 -3.058058 -0.769488 H -0.617755 -3.645881 -1.591092 C 1.122675 -2.854978 -0.616458 H 1.823040 -3.274463 -1.337287 C 1.659733 -2.172625 0.525019 C -3.471791 0.324303 -0.142196 O -4.530977 -0.527976 -0.063262 C -5.818931 0.031346 0.134500 H -6.095078 0.708874 -0.684472 H -5.882428 0.574230 1.087251 H -6.510321 -0.812939 0.153823 C -3.536317 1.713832 -0.017340 H -4.489242 2.201380 0.154924 C -2.374055 2.494807 -0.098639 H -2.455621 3.573350 0.012496 C -1.129453 1.910687 -0.322370 C 0.160887 2.697885 -0.419848 H 0.631369 2.469264 -1.384653 C 1.160347 2.364447 0.725585 H 0.935932 1.355706 1.098027 H 1.048276 3.060360 1.562583 C 2.622343 2.353197 0.299144 C 3.004543 1.410542 -0.821606 H 2.966853 1.834403 -1.826041 C 3.466694 0.161740 -0.650269 O 3.878622 -0.633526 -1.687379 H 3.775931 -0.146433 -2.521029 C 3.657874 -0.537122 0.670280 H 3.193025 0.054385 1.464904 H 4.734910 -0.558361 0.888210 C 3.141619 -2.002270 0.711529 H 3.680161 -2.581208 -0.044795 H 3.435005 -2.406309 1.692722 O 3.453506 3.064270 0.833197 H -0.043612 3.773874 -0.423238 C -1.071964 0.517014 -0.463522 H -0.124646 0.031583 -0.674595 ------------------------------------------------------------------------------


S104

S104


5.6.10 TSb→ba Supporting Information: E-9-desmethylgarugamblin-b-CO-mAnsa-c-scanIn-TS1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.00407711 Predicted Change= -1.375539D-10 ============================================================================== Optimization completed on the basis of negligible forces. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00252 || 0.00180 [ NO ] 0.00252 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -0.868652 -2.561050 -1.162560 H -1.318890 -2.699179 -2.143539 C 0.517853 -2.471793 -1.059172 H 1.150474 -2.502538 -1.941019 C 1.092289 -2.199810 0.183015 O 2.399898 -1.722519 0.235165 C 2.454103 -0.336779 0.088939 C 0.307325 -2.199763 1.335041 H 0.774909 -2.012347 2.296856 C -1.083426 -2.277427 1.214656 H -1.699493 -2.185891 2.106237 C -1.694943 -2.370703 -0.042496 C 3.712341 0.290912 0.035010 O 4.804209 -0.522490 0.125766 C 6.085237 0.081230 0.081276 H 6.229470 0.787245 0.910414 H 6.253830 0.605690 -0.869235 H 6.803483 -0.735583 0.174195 C 3.743438 1.684048 -0.110870 H 4.698829 2.194561 -0.162038 C 2.567095 2.442873 -0.191595 H 2.644628 3.522717 -0.295223 C 1.315195 1.826807 -0.129457 C 0.001299 2.606063 -0.126138 H -0.117364 3.108969 0.842712 C -1.249814 1.741454 -0.376055 H -1.202838 0.815540 0.201428 H -1.292066 1.436031 -1.431468 C -2.565266 2.405353 0.013621 C -3.762778 1.582405 0.305343 H -4.502780 2.175972 0.845325 C -4.109434 0.297955 0.032443 O -5.282843 -0.209490 0.513709 H -5.702942 0.449545 1.091594 C -3.476249 -0.727756 -0.873495 H -2.574121 -0.325497 -1.332391 H -4.203946 -0.868089 -1.683946 C -3.179233 -2.132968 -0.231911 H -3.713374 -2.222208 0.718384 H -3.595728 -2.900819 -0.893575 O -2.632301 3.617565 0.186518 H 0.039555 3.416059 -0.863371 C 1.303294 0.436702 -0.001271 H 0.358623 -0.071227 0.033446 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.00407711 Predicted Change= -1.375539D-10


5.6.11 TSb→bc Supporting Information: E-9-desmethylgarugamblin-b-CO-pAnsa-c-scanIn-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk UB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4(3) C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 3 ------------------------------------------------------------------------------ SCF Energy= -1074.90540231 Predicted Change= -1.230486D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00083 || 0.00180 [ YES ] 0.00083 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.537811 2.576120 -1.304105 H 2.053071 2.795479 -2.236894 C 0.142040 2.646030 -1.263185 H -0.435275 2.898011 -2.147592 C -0.519884 2.247472 -0.104393 O -1.883860 1.977204 -0.141551 C -2.144261 0.615943 -0.275544 C 0.197127 1.966251 1.059461 H -0.343200 1.702445 1.963408 C 1.587324 1.917049 1.009175 H 2.146049 1.642415 1.899680 C 2.272492 2.132551 -0.197677 C -3.380320 0.129613 0.193275 O -4.235881 1.055021 0.716459 C -5.488723 0.600243 1.196709 H -5.372255 -0.111678 2.025331 H -6.081199 0.129040 0.400686 H -6.010813 1.489020 1.556328 C -3.624234 -1.244842 0.106178 H -4.559155 -1.651264 0.475516 C -2.665128 -2.118417 -0.422250 H -2.878952 -3.183926 -0.445924 C -1.448213 -1.640293 -0.908897 C -0.410089 -2.556361 -1.538821 H -0.590335 -3.582706 -1.206560 C 1.064899 -2.204320 -1.243755 H 1.286554 -1.171227 -1.528268 H 1.699903 -2.829877 -1.889436 C 1.468646 -2.475679 0.200606 C 2.496276 -1.811314 0.913372 H 2.624653 -2.269446 1.895494 C 3.385943 -0.621659 0.708299 O 4.345164 -0.482148 1.685625 H 4.059000 -0.933031 2.496850 C 3.767085 0.125919 -0.527998 H 3.122068 -0.161596 -1.362007 H 4.799468 -0.141997 -0.809346 C 3.705297 1.680920 -0.344841 H 4.307106 1.948690 0.530664 H 4.173000 2.149548 -1.218618 O 0.837187 -3.366578 0.855606 H -0.537474 -2.549882 -2.631054 C -1.222483 -0.261806 -0.836841 H -0.292728 0.143484 -1.209969 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1074.90540231 Predicted Change= -1.230486D-09 Zero-point correction (ZPE)= -1074.5487 0.35669 Internal Energy (U)= -1074.5280 0.37732 Enthalpy (H)= -1074.5271 0.37826 Gibbs Free Energy (G)= -1074.5987 0.30664 ------------------------------------------------------------------------------


S105

S105

Frequencies -- -61.1143 17.4418 45.3755

5.6.12 TSc→ca Supporting Information: E-9-desmethylgarugamblin-c-pAnsa-CO-mAnsa-f-QST2TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # opt=(modredundant,maxcycle=250) b3lyp/6-31g(d) geom=connectivity gfinput gfprint scf=(direct,tight,maxcycle=300,xqc) Modredundant Input: D 6 20 25 36 F # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=allcheck guess=read #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1074.99953423 Predicted Change= -9.713526D-10 ============================================================================== Optimization completed. {Found 3 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00099 || 0.00180 [ YES ] 0.00099 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -0.868941 -2.285284 -0.972479 H -1.197121 -2.306796 -2.009864 C 0.492700 -2.194810 -0.703525 H 1.221754 -2.127117 -1.505335 C 0.919928 -2.064644 0.618451 O 2.222326 -1.624838 0.872316 C 2.346514 -0.265678 0.569215 C 0.015224 -2.234715 1.663332 H 0.367374 -2.181923 2.689311 C -1.351310 -2.302974 1.374946 H -2.062544 -2.298922 2.197815 C -1.818063 -2.221423 0.060068 C 3.415802 0.166343 -0.239048 O 4.313463 -0.786557 -0.624757 C 3.464471 1.517821 -0.602584 H 4.274920 1.883605 -1.223234 C 2.456039 2.406728 -0.205789 H 2.512423 3.442152 -0.535796 C 1.394616 1.983801 0.597457 C 0.267426 2.917483 1.019851 H -0.023027 2.687616 2.052203 C -1.019296 2.925105 0.149534 H -0.755738 3.051686 -0.911527 H -1.624220 3.806431 0.406208 C -1.895775 1.675006 0.245167 C -3.301872 1.740625 -0.187154 H -3.834067 2.685629 -0.074098 C -3.972992 0.657459 -0.663545 O -5.316898 0.689899 -0.876802 C -3.381228 -0.627329 -1.195450 H -2.387147 -0.393838 -1.576906 H -4.008740 -0.885080 -2.056299 C -3.266514 -1.887481 -0.258713 H -3.821550 -1.724991 0.670531 H -3.756750 -2.726426 -0.769019 O -1.438024 0.620881 0.669492 H 0.648771 3.946362 1.028447 C 1.396334 0.645165 1.009116 H 0.583153 0.283656 1.619509 H -5.680013 1.513820 -0.509717 C 5.406354 -0.379554 -1.428482 H 6.032447 0.363149 -0.915510 H 5.994366 -1.280942 -1.612050 H 5.072277 0.037000 -2.388889 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1074.99953423 Predicted Change= -9.713526D-10 Zero-point correction (ZPE)= -1074.6394 0.36005 Internal Energy (U)= -1074.6195 0.38000 Enthalpy (H)= -1074.6185 0.38095 Gibbs Free Energy (G)= -1074.6873 0.31222 ------------------------------------------------------------------------------ Frequencies -- -47.8166 22.0121 50.4027

5.6.13 TSc→cb Supporting Information: E-9-desmethylgarugamblin-c-pAnsa-CO-c-scanIn-afterbackSM-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.00191241 Predicted Change= -9.938585D-11 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00016 || 0.00180 [ YES ] 0.00016 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.100686 -2.647081 -1.245114 H -1.661344 -2.916834 -2.137581 C 0.293231 -2.582410 -1.313158 H 0.820995 -2.768422 -2.243615 C 1.004681 -2.147814 -0.197873 O 2.335497 -1.753544 -0.336189 C 2.452296 -0.366278 -0.334965 C 0.350838 -1.942249 1.018991 H 0.928936 -1.638790 1.886457 C -1.040381 -2.008609 1.071456 H -1.551083 -1.783212 2.004799 C -1.792842 -2.284776 -0.080010 C 3.650570 0.222378 0.119983 O 4.660138 -0.634533 0.445765 C 5.874013 -0.077526 0.919685 H 5.723802 0.490852 1.847733 H 6.338893 0.576783 0.169901 H 6.533581 -0.924413 1.117825 C 3.700361 1.616699 0.226361 H 4.605065 2.095952 0.583618 C 2.580036 2.412143 -0.065037 H 2.639773 3.486070 0.094185 C 1.402455 1.833907 -0.533273 C 0.087779 2.566817 -0.742991 H 0.200086 3.639946 -0.556584 C -0.998613 1.975876 0.182167 H -0.816180 2.278130 1.225476 H -0.935668 0.882149 0.214810 C -2.440176 2.334450 -0.130809 C -3.480955 1.620920 0.700166 H -3.926316 2.256812 1.468180 C -3.947023 0.366026 0.565802 O -4.899364 -0.148988 1.410559 H -5.090974 0.500674 2.106182 C -3.674749 -0.613501 -0.549377 H -2.921137 -0.205218 -1.229106 H -4.611173 -0.667958 -1.121378 C -3.289421 -2.067731 -0.118117 H -3.749042 -2.284763 0.850992 H -3.736542 -2.760013 -0.840194 O -2.745369 3.205533 -0.925685 H -0.246869 2.471373 -1.784073 C 1.393998 0.446240 -0.713831 H 0.495504 -0.021760 -1.093586 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.00191241 Predicted Change= -9.938585D-11 Zero-point correction (ZPE)= -1074.6422 0.35969 Internal Energy (U)= -1074.6220 0.37989 Enthalpy (H)= -1074.6210 0.38083 Gibbs Free Energy (G)= -1074.6905 0.31137 ------------------------------------------------------------------------------ Frequencies -- -64.2355 30.7573 42.8700


S106

S106

5.6.14 Intab Supporting Information: E-9-desmethylgarugamblin-a-mAnsa-CO-c-scanIn-switchAtoms-GS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.01194628 Predicted Change= -5.429425D-09 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00229 || 0.00180 [ NO ] 0.00229 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.482862 -2.548822 -1.280563 H -1.986552 -2.782406 -2.216241 C -0.090342 -2.640600 -1.214455 H 0.497732 -2.915721 -2.084759 C 0.558272 -2.228355 -0.052517 O 1.922475 -1.957466 -0.080200 C 2.175374 -0.597660 -0.250492 C -0.173914 -1.916474 1.093793 H 0.354302 -1.637066 2.000106 C -1.561843 -1.843222 1.018200 H -2.128789 -1.532392 1.891645 C -2.229146 -2.069101 -0.195736 C 3.419602 -0.093586 0.174275 O 4.297620 -1.001922 0.690300 C 5.556104 -0.526261 1.134072 H 5.450448 0.200015 1.951550 H 6.126277 -0.064479 0.316474 H 6.094907 -1.403021 1.498506 C 3.648398 1.281481 0.054511 H 4.589952 1.701801 0.390127 C 2.666701 2.139332 -0.458830 H 2.869929 3.206342 -0.502062 C 1.440014 1.642789 -0.900067 C 0.361295 2.537671 -1.494432 H 0.506293 3.560039 -1.134184 C -1.091048 2.115679 -1.186984 H -1.273293 1.080450 -1.485290 H -1.774738 2.723151 -1.799269 C -1.485434 2.349659 0.272245 C -2.630924 1.694111 0.939712 H -2.730460 2.116731 1.941827 C -3.535505 0.731618 0.627600 O -4.471728 0.371925 1.558117 H -4.338008 0.897250 2.364914 C -3.765975 -0.088656 -0.614598 H -3.085302 0.210103 -1.412319 H -4.786773 0.135289 -0.952784 C -3.663759 -1.630506 -0.376978 H -4.279319 -1.891020 0.489731 H -4.103337 -2.128647 -1.248494 O -0.856309 3.171751 0.932163 H 0.473744 2.566403 -2.587962 C 1.233132 0.263856 -0.802576 H 0.297680 -0.154841 -1.141648 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.01194628 Predicted Change= -5.429425D-09 Zero-point correction (ZPE)= -1074.6508 0.36112 Internal Energy (U)= -1074.6301 0.38174 Enthalpy (H)= -1074.6292 0.38269 Gibbs Free Energy (G)= -1074.7009 0.31101 ------------------------------------------------------------------------------ Frequencies -- 8.6993 38.0213 49.4892

5.6.15 Intca Supporting Information: E-9-desmethylgarugamblin-c-pAnsa-CO-mAnsa-g-GS.log

------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # opt=maxcycle=250 freq=noraman b3lyp/6-31g(d) geom=connectivity gfinput gfprint scf=(direct,tight,maxcycle=300,xqc) #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.02543786 Predicted Change= -1.615699D-08 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00125 || 0.00180 [ YES ] 0.00125 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.477976 -1.912546 1.337819 H 1.870902 -1.742958 2.336874 C 0.101769 -1.951381 1.148029 H -0.583606 -1.805785 1.976903 C -0.405716 -2.069025 -0.146398 O -1.761798 -1.846591 -0.365749 C -2.111867 -0.506678 -0.323375 C 0.444026 -2.288147 -1.226361 H 0.024649 -2.405149 -2.221070 C 1.825895 -2.241820 -1.020672 H 2.495398 -2.334243 -1.872723 C 2.358328 -1.986723 0.248346 C -3.469994 -0.199917 -0.089869 O -4.307546 -1.265351 0.061794 C -3.847289 1.142955 -0.024225 H -4.882592 1.406071 0.161141 C -2.900678 2.164624 -0.181372 H -3.226693 3.199864 -0.114475 C -1.560797 1.868531 -0.425172 C -0.514570 2.950362 -0.613382 H 0.016108 2.787899 -1.561728 C 0.517993 3.093792 0.537525 H -0.003018 3.214635 1.491531 H 1.092353 4.014981 0.354342 C 1.542896 1.967693 0.746323 C 2.417190 1.653780 -0.398077 H 2.215936 2.209287 -1.315010 C 3.449410 0.768790 -0.429679 O 4.172722 0.574239 -1.564447 C 3.975724 -0.089404 0.686744 H 3.463348 0.195714 1.605502 H 5.046110 0.132863 0.794987 C 3.813340 -1.617092 0.426808 H 4.392525 -1.900646 -0.458102 H 4.252601 -2.142132 1.284178 O 1.627401 1.428235 1.846451 H -1.020656 3.917677 -0.717311 C -1.190513 0.519048 -0.505345 H -0.156954 0.265302 -0.704358 H 3.806499 1.121625 -2.279879 C -5.678079 -1.000357 0.304104 H -6.136242 -0.444356 -0.525235 H -6.159346 -1.976123 0.393056 H -5.823821 -0.437693 1.236353 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.02543786 Predicted Change= -1.615699D-08 Zero-point correction (ZPE)= -1074.6642 0.36118 Internal Energy (U)= -1074.6436 0.38177 Enthalpy (H)= -1074.6427 0.38271 Gibbs Free Energy (G)= -1074.7130 0.31235 ------------------------------------------------------------------------------ Frequencies -- 26.4850 47.2335 69.6754

5.6.16 TSca→cab Supporting Information: E-9-desmethylgarugamblin-c-pAnsa-CO-mAnsa-h-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ==============================================================================


S107

S107

# b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,modredundant) geom=connectivity Modredundant Input: D 23 24 26 29 F # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=allcheck guess=read #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.01206112 Predicted Change= -3.538378D-12 ============================================================================== Optimization completed. {Found 3 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00003 || 0.00180 [ YES ] 0.00003 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.128297 -2.053371 1.256201 H 1.313913 -2.022855 2.327392 C -0.178407 -2.001736 0.791344 H -1.015384 -1.926349 1.477974 C -0.412831 -1.934465 -0.583744 O -1.687391 -1.625475 -1.046881 C -2.100196 -0.365442 -0.626469 C 0.634047 -2.077084 -1.489282 H 0.424298 -2.062138 -2.554588 C 1.944584 -2.129567 -1.005530 H 2.772084 -2.158106 -1.710979 C 2.211181 -2.044293 0.365609 C -3.384113 -0.238427 -0.064240 O -4.136227 -1.374965 -0.006964 C -5.432089 -1.281210 0.558402 H -6.070213 -0.585936 -0.003784 H -5.394857 -0.963087 1.609305 H -5.855864 -2.285623 0.501032 C -3.774080 1.016292 0.412678 H -4.748916 1.148854 0.868467 C -2.900732 2.105792 0.341342 H -3.227534 3.063324 0.739768 C -1.632520 1.993892 -0.235543 C -0.778805 3.237606 -0.414744 H -0.913120 3.579278 -1.450382 C 0.770167 3.232851 -0.152306 H 0.975899 3.992609 0.612721 H 1.277087 3.579089 -1.058134 C 1.486573 1.978324 0.378384 C 2.653547 1.551930 -0.417861 H 2.780571 2.064462 -1.371925 C 3.601599 0.631942 -0.096099 O 4.626560 0.361977 -0.948720 C 3.725213 -0.194046 1.151431 H 2.959957 0.129990 1.857845 H 4.716943 0.003582 1.580918 C 3.594254 -1.724162 0.880231 H 4.365081 -2.034885 0.167380 H 3.793194 -2.244662 1.824914 O 1.129173 1.456722 1.429219 H -1.221900 4.025827 0.202391 C -1.260151 0.739489 -0.732374 H -0.282871 0.593642 -1.180305 H 4.521484 0.891018 -1.757834 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.01206112 Predicted Change= -3.538378D-12 Zero-point correction (ZPE)= -1074.6514 0.36063 Internal Energy (U)= -1074.6313 0.38070 Enthalpy (H)= -1074.6304 0.38164 Gibbs Free Energy (G)= -1074.6999 0.31214 ------------------------------------------------------------------------------ Frequencies -- -171.5188 22.1803 40.1966

5.6.17 ent- C9-E-9’-

Desmethylgarugamblin I Supporting Information: E-9-desmethylgarugamblin-a-mAnsa-pAnsa-c-scanIn-switchAtoms-GS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011

============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C20H20O4 C1[X(C20H20O4)] #Atoms= 44 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1075.02921936 Predicted Change= -4.916743D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00297 || 0.00180 [ NO ] 0.00297 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.600907 -1.890046 1.002124 H 2.119317 -1.745272 1.947096 C 0.208480 -1.917321 0.980469 H -0.372101 -1.781181 1.887715 C -0.453790 -2.032815 -0.241553 O -1.828315 -1.831227 -0.294785 C -2.196521 -0.494551 -0.239465 C 0.260465 -2.253126 -1.416822 H -0.276457 -2.368808 -2.353242 C 1.654536 -2.217152 -1.380302 H 2.212517 -2.316184 -2.308676 C 2.342233 -1.971823 -0.184834 C -3.511586 -0.202570 0.180829 O -4.301305 -1.275747 0.476926 C -5.632694 -1.022322 0.887282 H -6.202011 -0.491705 0.111917 H -5.667111 -0.439250 1.818060 H -6.083964 -2.001442 1.059213 C -3.896805 1.136622 0.270656 H -4.898806 1.391399 0.597683 C -2.996302 2.166570 -0.037086 H -3.324064 3.198755 0.062507 C -1.701015 1.883844 -0.467623 C -0.696877 2.975653 -0.792062 H -0.351497 2.875582 -1.828000 C 0.551035 2.985059 0.117535 H 0.266994 2.828388 1.165330 H 1.021606 3.980344 0.077010 C 1.654890 1.989567 -0.279816 C 2.592567 1.636575 0.796626 H 2.421570 2.137986 1.750253 C 3.607613 0.734049 0.745024 O 4.370058 0.476860 1.841744 H 4.061392 1.021390 2.585973 C 4.051088 -0.109595 -0.416185 H 5.128470 0.058845 -0.546799 H 3.529370 0.228480 -1.311685 C 3.815828 -1.636902 -0.198002 H 4.321218 -2.164824 -1.015009 H 4.299305 -1.946206 0.735051 O 1.730743 1.569704 -1.432418 H -1.193636 3.949182 -0.711627 C -1.328147 0.536008 -0.579565 H -0.336982 0.293456 -0.937903 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1075.02921936 Predicted Change= -4.916743D-08 Zero-point correction (ZPE)= -1074.6681 0.36108 Internal Energy (U)= -1074.6474 0.38172 Enthalpy (H)= -1074.6465 0.38266 Gibbs Free Energy (G)= -1074.7172 0.31193 ------------------------------------------------------------------------------ Frequencies -- 23.6093 39.0033 65.4014


5.7.1 C9-E-Garugamblin I Supporting Information: E-Garugamblin-a-mAnsa-CO-pAnsa-a-GS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity


S108

S108

#N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.33555306 Predicted Change= -1.748719D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00338 || 0.00180 [ NO ] 0.00338 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.409601 -1.945925 0.890823 H 2.011296 -1.765515 1.778681 C 0.020331 -1.915379 0.986706 H -0.475520 -1.697568 1.927726 C -0.747256 -2.080659 -0.165677 O -2.112627 -1.821722 -0.119627 C -2.423775 -0.469779 -0.151591 C -0.144163 -2.405024 -1.378584 H -0.763021 -2.555861 -2.257622 C 1.248314 -2.424269 -1.460500 H 1.721156 -2.603994 -2.423356 C 2.044198 -2.131882 -0.345248 C -3.697229 -0.088838 0.322916 O -4.506271 -1.099986 0.755042 C -5.796313 -0.756664 1.227488 H -6.397014 -0.268119 0.448110 H -5.745758 -0.097526 2.105257 H -6.271038 -1.697979 1.511203 C -4.025653 1.268217 0.324648 H -4.994536 1.590412 0.689543 C -3.109503 2.231193 -0.122276 H -3.391868 3.280930 -0.089785 C -1.855876 1.859984 -0.605363 C -0.835197 2.878203 -1.082031 H -0.569240 2.685058 -2.128255 C 0.474401 2.898628 -0.264656 H 0.261541 2.825123 0.808734 H 0.976196 3.869017 -0.407624 C 1.511969 1.834387 -0.667017 C 2.511319 1.523866 0.369235 H 2.414322 2.106101 1.279132 C 3.486887 0.576816 0.308335 O 4.344151 0.332987 1.331225 C 4.252389 1.091602 2.532922 H 4.415578 2.158466 2.339851 H 5.041302 0.711319 3.183566 H 3.277214 0.953823 3.014855 C 3.793462 -0.357004 -0.832875 H 4.860835 -0.244803 -1.065441 H 3.210288 -0.051439 -1.701507 C 3.522063 -1.856999 -0.501201 H 3.937281 -2.454441 -1.321276 H 4.070914 -2.128782 0.407088 O 1.485304 1.337115 -1.790549 H -1.286558 3.876150 -1.044091 C -1.540657 0.492948 -0.626259 H -0.583693 0.181942 -1.022283 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.33555306 Predicted Change= -1.748719D-08 Zero-point correction (ZPE)= -1113.9458 0.38973 Internal Energy (U)= -1113.9237 0.41183 Enthalpy (H)= -1113.9227 0.41278 Gibbs Free Energy (G)= -1113.9968 0.33873 ------------------------------------------------------------------------------ Frequencies -- 23.0856 32.1064 62.8834

5.7.2 TSa Supporting Information: E-Garugamblin-a-mAnsa-CO-pAnsa-b-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------

Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.31760693 Predicted Change= -1.322800D-11 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00003 || 0.00180 [ YES ] 0.00003 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.166960 -2.180761 0.816467 H 1.519605 -2.176701 1.845443 C -0.199058 -2.126747 0.558386 H -0.925088 -2.073570 1.363904 C -0.638623 -2.031989 -0.762247 O -1.965064 -1.688499 -1.017541 C -2.231370 -0.387214 -0.602382 C 0.256663 -2.163066 -1.820087 H -0.111824 -2.124859 -2.840481 C 1.623449 -2.212915 -1.545124 H 2.329597 -2.212673 -2.371788 C 2.098337 -2.142289 -0.230149 C -3.325549 -0.171695 0.255272 O -4.066482 -1.269128 0.583264 C -5.187961 -1.081140 1.428701 H -5.921261 -0.395827 0.982563 H -4.893990 -0.697666 2.415604 H -5.641183 -2.067214 1.546527 C -3.547133 1.124835 0.730251 H -4.371137 1.326217 1.405788 C -2.687398 2.166944 0.372333 H -2.874732 3.159362 0.776347 C -1.609401 1.966170 -0.496935 C -0.785438 3.167269 -0.938114 H -1.228037 3.543609 -1.870122 C 0.765584 3.080470 -1.195497 H 1.244530 3.859087 -0.588159 H 0.955316 3.333101 -2.241576 C 1.564482 1.782764 -0.977304 C 1.970642 1.479020 0.403335 H 1.475108 2.070651 1.165713 C 2.918985 0.579400 0.785967 O 3.245707 0.355246 2.082898 C 2.533306 1.027419 3.117133 H 2.687279 2.111802 3.061704 H 2.943751 0.647951 4.054219 H 1.460788 0.808095 3.063631 C 3.788496 -0.272960 -0.104473 H 4.834006 -0.060953 0.157782 H 3.615644 0.020719 -1.139381 C 3.542250 -1.804613 0.055383 H 4.218800 -2.320913 -0.636396 H 3.817120 -2.111844 1.070232 O 1.884891 1.117365 -1.960838 H -0.960213 3.961714 -0.204173 C -1.413003 0.671077 -0.992838 H -0.591809 0.460161 -1.668124 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.31760693 Predicted Change= -1.322800D-11 Zero-point correction (ZPE)= -1113.9280 0.38954 Internal Energy (U)= -1113.9066 0.41098 Enthalpy (H)= -1113.9056 0.41193 Gibbs Free Energy (G)= -1113.9783 0.33927 ------------------------------------------------------------------------------ Frequencies -- -165.9102 17.0671 37.4933

5.7.3 TSb Supporting Information: E-Garugamblin-b-CO-mAnsa-pAnsa-b3-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) gfinput opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1


S109

S109

------------------------------------------------------------------------------ SCF Energy= -1114.30971863 Predicted Change= -4.988623D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00468 || 0.00180 [ NO ] 0.00468 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.704069 -2.006149 1.044584 H 1.264328 -1.726744 1.933951 C -0.684832 -1.895903 1.049127 H -1.210821 -1.507436 1.915804 C -1.401694 -2.163061 -0.119795 O -2.719801 -1.720122 -0.232959 C -2.773169 -0.327937 -0.293184 C -0.756947 -2.707097 -1.228155 H -1.332334 -2.942076 -2.118483 C 0.636131 -2.816365 -1.216586 H 1.145362 -3.171866 -2.109971 C 1.393174 -2.390400 -0.114872 C -3.895874 0.346160 0.226023 O -4.925684 -0.434051 0.662541 C -6.065789 0.213907 1.200057 H -6.543425 0.871368 0.461190 H -5.814879 0.801551 2.093707 H -6.759379 -0.582756 1.475482 C -3.852265 1.744654 0.281915 H -4.694689 2.292013 0.690168 C -2.709278 2.456321 -0.115128 H -2.688034 3.535160 0.018714 C -1.605677 1.792804 -0.650763 C -0.267764 2.451430 -0.957334 H -0.098485 2.530180 -2.040019 C 0.879879 1.641597 -0.319185 H 0.944344 0.641358 -0.755101 H 0.646420 1.454670 0.739372 C 2.258769 2.279271 -0.334922 C 3.408761 1.511010 0.224037 H 4.064564 2.171236 0.784121 C 3.791447 0.216533 0.092875 O 4.872907 -0.295330 0.750755 C 5.543143 0.492897 1.725921 H 6.051348 1.349317 1.265754 H 6.284274 -0.166196 2.181396 H 4.845579 0.855292 2.490675 C 3.299295 -0.845270 -0.865868 H 4.148584 -1.022058 -1.539163 H 2.492042 -0.456362 -1.488343 C 2.892397 -2.223339 -0.236092 H 3.295163 -3.016477 -0.875754 H 3.382728 -2.329555 0.736452 O 2.416747 3.453438 -0.643793 H -0.247129 3.476065 -0.573048 C -1.703046 0.404213 -0.786896 H -0.873289 -0.139810 -1.213816 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.30971863 Predicted Change= -4.988623D-08 Zero-point correction (ZPE)= -1113.9207 0.38896 Internal Energy (U)= -1113.8991 0.41052 Enthalpy (H)= -1113.8982 0.41147 Gibbs Free Energy (G)= -1113.9713 0.33837 ------------------------------------------------------------------------------ Frequencies -- -50.9883 21.3525 36.6082

5.7.4 TSc Supporting Information: E-Garugamblin-c-pAnsa-CO-mAnsa-b2-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.29547746 Predicted Change= -7.752017D-11

============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00073 || 0.00180 [ YES ] 0.00073 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -0.368702 -2.744573 -0.994878 H -0.702674 -2.805331 -2.029316 C 0.953257 -2.395672 -0.728577 H 1.659692 -2.210414 -1.532137 C 1.334001 -2.130014 0.589034 O 2.513952 -1.439938 0.842406 C 2.459987 -0.099737 0.454256 C 0.485876 -2.464128 1.643021 H 0.822409 -2.324232 2.665743 C -0.838344 -2.808610 1.359996 H -1.542648 -2.904664 2.184023 C -1.313752 -2.823556 0.041041 C 3.508418 0.380351 -0.355527 O 4.463882 -0.526793 -0.710026 C 5.554994 -0.067812 -1.488759 H 6.120571 0.717663 -0.969592 H 5.226222 0.313832 -2.465277 H 6.199346 -0.935907 -1.640241 C 3.489431 1.723022 -0.742816 H 4.281895 2.123220 -1.365323 C 2.446152 2.562938 -0.340502 H 2.464420 3.603999 -0.655330 C 1.399268 2.103027 0.463263 C 0.312756 3.067797 0.927055 H 0.127741 2.925127 1.996733 C -1.053515 2.990207 0.202233 H -0.923498 2.848276 -0.878645 H -1.584695 3.948748 0.312128 C -1.974505 1.889153 0.737841 C -3.197636 1.565503 -0.051724 H -3.760191 2.404630 -0.451017 C -3.502443 0.287030 -0.402020 O -4.569806 -0.099051 -1.133532 C -5.545696 0.882545 -1.469745 H -5.924353 1.380518 -0.569352 H -6.354242 0.345834 -1.968155 H -5.127591 1.634023 -2.151233 C -2.492860 -0.804784 -0.158334 H -2.069638 -0.607115 0.823012 H -1.680612 -0.595718 -0.865930 C -2.733031 -2.337576 -0.237432 H -3.450597 -2.673888 0.519332 H -3.101403 -2.645176 -1.221919 O -1.676738 1.296705 1.769005 H 0.697517 4.086800 0.804088 C 1.431345 0.751806 0.856890 H 0.642008 0.360859 1.489701 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.29547746 Predicted Change= -7.752017D-11 Zero-point correction (ZPE)= -1113.9070 0.38838 Internal Energy (U)= -1113.8855 0.40994 Enthalpy (H)= -1113.8845 0.41088 Gibbs Free Energy (G)= -1113.9574 0.33801 ------------------------------------------------------------------------------ Frequencies -- -123.6896 15.4221 42.4449

5.7.5 Inta Supporting Information: E-Garugamblin-a-mAnsa-CO-pAnsa-c-GS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.33181919 Predicted Change= -6.054156D-09 ============================================================================== Optimization completed. {Found 2 times}


S110

S110

Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00103 || 0.00180 [ YES ] 0.00103 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.606038 -2.303031 0.938780 H 2.317571 -2.370276 1.758667 C 0.237298 -2.274728 1.220205 H -0.130353 -2.304704 2.241456 C -0.662083 -2.094014 0.173809 O -1.993441 -1.797137 0.449065 C -2.288728 -0.447371 0.347952 C -0.223243 -2.088207 -1.150457 H -0.947330 -1.971135 -1.950485 C 1.141141 -2.120746 -1.415040 H 1.484386 -2.035991 -2.442696 C 2.077327 -2.157511 -0.371331 C -3.648685 -0.093517 0.209875 O -4.538768 -1.126920 0.199343 C -5.912875 -0.814584 0.054264 H -6.114826 -0.305473 -0.898102 H -6.275359 -0.186966 0.879888 H -6.439461 -1.770700 0.070498 C -3.975806 1.258387 0.089257 H -5.011878 1.556629 -0.025274 C -2.978881 2.243805 0.101173 H -3.267771 3.286802 -0.004359 C -1.636019 1.902428 0.250020 C -0.535958 2.946699 0.284013 H -0.996089 3.940905 0.335007 C 0.428851 2.948579 -0.931687 H 1.042699 3.860329 -0.865253 H -0.144007 3.006365 -1.861577 C 1.408641 1.774730 -1.102220 C 2.315725 1.511151 0.031713 H 2.158194 2.141032 0.900226 C 3.315086 0.587212 0.082487 O 4.101275 0.405649 1.172405 C 3.872730 1.174560 2.349058 H 4.022947 2.243884 2.158200 H 4.606988 0.826617 3.077261 H 2.860140 1.011800 2.736363 C 3.744222 -0.360130 -1.007937 H 4.815452 -0.194232 -1.185414 H 3.196321 -0.107088 -1.915231 C 3.533637 -1.861169 -0.649099 H 3.903251 -2.455055 -1.494449 H 4.148378 -2.117696 0.219965 O 1.428423 1.166668 -2.169070 H 0.044105 2.839561 1.211036 C -1.314282 0.544433 0.383607 H -0.278098 0.257456 0.509683 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.33181919 Predicted Change= -6.054156D-09 Zero-point correction (ZPE)= -1113.9420 0.38976 Internal Energy (U)= -1113.9199 0.41182 Enthalpy (H)= -1113.9190 0.41276 Gibbs Free Energy (G)= -1113.9928 0.33895 ------------------------------------------------------------------------------ Frequencies -- 22.8303 36.4228 68.5563

5.7.6 Intb Supporting Information: E-Garugamblin-b-CO-mAnsa-pAnsa-c-GS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.31753078 Predicted Change= -1.490153D-08 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00146 || 0.00180 [ YES ] 0.00146 || 0.00180 [ YES ]

------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.313027 -1.877408 0.897435 H 1.949373 -1.528075 1.705921 C -0.067998 -1.887306 1.070124 H -0.521465 -1.520491 1.985694 C -0.889083 -2.249096 0.001183 O -2.240808 -1.921304 0.043868 C -2.443597 -0.560859 -0.182758 C -0.338206 -2.770977 -1.166974 H -0.994719 -3.082546 -1.973752 C 1.049080 -2.743255 -1.331086 H 1.477925 -3.064863 -2.277902 C 1.886369 -2.217935 -0.337474 C -3.609260 0.037154 0.332398 O -4.477942 -0.789072 0.984678 C -5.648784 -0.213426 1.536581 H -6.281489 0.241130 0.762050 H -5.409314 0.545515 2.293921 H -6.191579 -1.034929 2.008147 C -3.773481 1.415884 0.158228 H -4.651916 1.908577 0.560070 C -2.800986 2.186842 -0.492229 H -2.946297 3.261222 -0.570904 C -1.653641 1.596147 -1.022154 C -0.583261 2.391966 -1.755330 H -0.772796 2.347643 -2.837677 C 0.866016 1.917579 -1.516947 H 1.533529 2.443681 -2.216389 H 0.976465 0.856474 -1.751449 C 1.374789 2.227050 -0.107711 C 2.553453 1.587021 0.523232 H 2.729899 2.087906 1.469373 C 3.399613 0.571630 0.210953 O 4.420245 0.213908 1.044462 C 4.635781 0.910683 2.266586 H 4.845127 1.971848 2.087651 H 5.506086 0.436277 2.723151 H 3.772832 0.820432 2.936998 C 3.472772 -0.340012 -0.991180 H 4.465989 -0.192952 -1.436149 H 2.736019 -0.057021 -1.743139 C 3.320945 -1.857061 -0.646778 H 3.672990 -2.430241 -1.512038 H 3.987673 -2.091664 0.188950 O 0.815973 3.107845 0.540064 H -0.656028 3.443370 -1.463440 C -1.517343 0.213138 -0.873669 H -0.645279 -0.278872 -1.278260 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.31753078 Predicted Change= -1.490153D-08 Zero-point correction (ZPE)= -1113.9275 0.38995 Internal Energy (U)= -1113.9055 0.41196 Enthalpy (H)= -1113.9046 0.41291 Gibbs Free Energy (G)= -1113.9789 0.33858 ------------------------------------------------------------------------------ Frequencies -- 14.0245 31.3499 48.9127

5.7.7 Intc Supporting Information: E-Garugamblin-c-pAnsa-CO-mAnsa-e-GS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.30751140 Predicted Change= -2.158302D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00348 || 0.00180 [ NO ] 0.00348 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z


S111

S111

------------------------------------------------------------------------------ C -0.610750 -2.492595 -1.002354 H -1.043015 -2.580215 -1.997153 C 0.765497 -2.328355 -0.880851 H 1.405248 -2.266904 -1.756018 C 1.315666 -2.114695 0.383573 O 2.607658 -1.600289 0.477601 C 2.642137 -0.218761 0.297119 C 0.531820 -2.267597 1.523664 H 0.981738 -2.135752 2.502992 C -0.852674 -2.401142 1.382542 H -1.476923 -2.372920 2.271765 C -1.452185 -2.411670 0.120058 C 3.825289 0.349299 -0.219176 O 4.847047 -0.515346 -0.487355 C 6.053618 0.024446 -0.994841 H 6.505641 0.738683 -0.292964 H 5.901163 0.522612 -1.962401 H 6.727555 -0.823949 -1.129272 C 3.860190 1.731650 -0.426198 H 4.753960 2.195383 -0.828597 C 2.749268 2.535645 -0.132629 H 2.816114 3.606864 -0.310002 C 1.580495 1.981617 0.391023 C 0.384079 2.841592 0.780610 H 0.163469 2.689627 1.845105 C -0.937587 2.648944 -0.008971 H -0.728678 2.520547 -1.081688 H -1.540546 3.566216 0.055877 C -1.823277 1.475816 0.414246 C -3.232290 1.459624 -0.045530 H -3.786512 2.388613 0.052348 C -3.844108 0.341557 -0.513077 O -5.178622 0.255022 -0.753717 C -6.023045 1.316155 -0.324279 H -5.875839 1.529567 0.741273 H -7.045074 0.976166 -0.499535 H -5.838913 2.228916 -0.905189 C -3.145927 -0.900551 -1.021226 H -2.170064 -0.591284 -1.397225 H -3.731101 -1.221140 -1.890023 C -2.934260 -2.129282 -0.062467 H -3.393139 -1.937604 0.911943 H -3.454201 -2.995671 -0.490277 O -1.398147 0.570937 1.122772 H 0.674198 3.893691 0.673950 C 1.559794 0.595947 0.604977 H 0.660915 0.160106 1.013408 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.30751140 Predicted Change= -2.158302D-08 Zero-point correction (ZPE)= -1113.9187 0.38871 Internal Energy (U)= -1113.8964 0.41109 Enthalpy (H)= -1113.8954 0.41204 Gibbs Free Energy (G)= -1113.9703 0.33719 ------------------------------------------------------------------------------ Frequencies -- 21.6918 35.5960 49.9469

5.7.8 TSa→ab Supporting Information: E-Garugamblin-a-mAnsa-CO-pAnsa-d-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.31121864 Predicted Change= -8.444164D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00119 || 0.00180 [ YES ] 0.00119 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.278256 -2.492690 0.591660

H 2.035474 -2.644703 1.356007 C -0.069830 -2.449073 0.958993 H -0.373243 -2.543963 1.997297 C -1.025118 -2.145015 -0.006667 O -2.307193 -1.757959 0.381969 C -2.454178 -0.376203 0.353247 C -0.667311 -2.053572 -1.352974 H -1.435132 -1.852870 -2.093878 C 0.678615 -2.103873 -1.704758 H 0.962560 -1.969796 -2.746587 C 1.677121 -2.243653 -0.728072 C -3.753513 0.162518 0.231825 O -4.777947 -0.736852 0.207661 C -6.097478 -0.234789 0.083834 H -6.235656 0.313779 -0.857842 H -6.360643 0.422506 0.923617 H -6.751105 -1.108966 0.091328 C -3.888109 1.550419 0.128428 H -4.874221 1.988392 0.021791 C -2.765307 2.394067 0.121987 H -2.909486 3.464990 0.001802 C -1.485295 1.865366 0.260025 C -0.198576 2.669638 0.222981 H -0.407634 3.742525 0.155964 C 0.735203 2.250441 -0.958671 H 0.515841 2.850306 -1.847316 H 0.544682 1.198651 -1.201036 C 2.218295 2.391693 -0.637893 C 2.805130 1.473025 0.413081 H 2.884272 1.936820 1.392633 C 3.347186 0.258169 0.207975 O 3.964818 -0.477823 1.182637 C 4.031045 0.053407 2.496843 H 4.596434 0.993929 2.517058 H 4.547932 -0.695723 3.099447 H 3.027355 0.226977 2.906162 C 3.458917 -0.463151 -1.116723 H 4.495398 -0.355111 -1.466439 H 2.826593 0.038885 -1.856438 C 3.125096 -1.981895 -1.077050 H 3.358544 -2.394183 -2.066426 H 3.789995 -2.470275 -0.359057 O 2.905149 3.254967 -1.154155 H 0.334549 2.515220 1.170931 C -1.363143 0.479158 0.409111 H -0.373160 0.060024 0.532996 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.31121864 Predicted Change= -8.444164D-09 Zero-point correction (ZPE)= -1113.9222 0.38892 Internal Energy (U)= -1113.9008 0.41038 Enthalpy (H)= -1113.8998 0.41133 Gibbs Free Energy (G)= -1113.9718 0.33932 ------------------------------------------------------------------------------ Frequencies -- -63.3381 33.7008 44.2572

5.7.9 TSa→acb Supporting Information: E-Garugamblin-a-mAnsa-pAnsa-CO-d-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.30650388 Predicted Change= -2.840445D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00041 || 0.00180 [ YES ] 0.00041 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.737270 -2.475165 1.358924 H 1.268430 -2.557754 2.303848 C -0.654753 -2.383937 1.372649


S112

S112

H -1.205992 -2.380664 2.308047 C -1.325400 -2.116156 0.181597 O -2.634375 -1.638708 0.207451 C -2.680227 -0.247813 0.181447 C -0.641746 -2.150049 -1.031654 H -1.188972 -1.987115 -1.955221 C 0.746580 -2.267163 -1.028877 H 1.267923 -2.236961 -1.982183 C 1.466039 -2.320441 0.173179 C -3.878174 0.365631 -0.240884 O -4.904553 -0.472929 -0.569466 C -6.123773 0.110032 -0.991334 H -5.994523 0.705753 -1.905646 H -6.561304 0.746299 -0.209776 H -6.798554 -0.723266 -1.197063 C -3.921534 1.761521 -0.303155 H -4.827140 2.259089 -0.632281 C -2.803133 2.537364 0.037151 H -2.872659 3.620468 -0.035607 C -1.622019 1.934936 0.468970 C -0.391572 2.732409 0.873178 H -0.631652 3.799729 0.800193 C 0.896606 2.482272 0.046589 H 1.513832 3.391770 0.046494 H 0.643410 2.308752 -1.009697 C 1.794618 1.317244 0.488209 C 3.174342 1.336056 -0.040816 H 3.610396 2.329092 -0.096669 C 3.941747 0.289083 -0.441355 O 5.253494 0.458879 -0.780190 C 5.884655 1.714520 -0.568041 H 5.472026 2.486141 -1.230549 H 6.938285 1.559403 -0.806391 H 5.781472 2.038718 0.474523 C 3.572042 -1.143000 -0.814069 H 4.505825 -1.565971 -1.193160 H 2.905145 -1.075343 -1.679382 C 2.975545 -2.143803 0.220674 H 3.462856 -3.111054 0.034091 H 3.262844 -1.846808 1.233687 O 1.406266 0.453921 1.265618 H -0.160449 2.536914 1.928424 C -1.592764 0.536852 0.544618 H -0.683952 0.071153 0.894999 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.30650388 Predicted Change= -2.840445D-10 Zero-point correction (ZPE)= -1113.9177 0.38877 Internal Energy (U)= -1113.8962 0.41029 Enthalpy (H)= -1113.8952 0.41124 Gibbs Free Energy (G)= -1113.9675 0.33893 ------------------------------------------------------------------------------ Frequencies -- -49.2210 22.1882 44.1428

5.7.10 TSb→ba Supporting Information: E-Garugamblin-b-CO-mAnsa-pAnsa-d-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.31116141 Predicted Change= 3.226889D-07 ============================================================================== Optimization completed on the basis of negligible forces. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.07619 || 0.00180 [ NO ] 0.07619 || 0.00180 [ NO ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.760435 -2.023038 1.070298 H 1.336521 -1.745495 1.950111 C -0.628420 -1.910724 1.099111 H -1.138865 -1.521803 1.974777 C -1.364547 -2.173723 -0.058619

O -2.681750 -1.728761 -0.151630 C -2.743595 -0.337917 -0.228110 C -0.739998 -2.717732 -1.178472 H -1.331365 -2.948947 -2.059248 C 0.652305 -2.830994 -1.190707 H 1.145876 -3.185198 -2.093378 C 1.428145 -2.406523 -0.101921 C -3.899942 0.323157 0.223367 O -4.934591 -0.466963 0.631646 C -6.110233 0.170892 1.099416 H -6.564834 0.801716 0.323591 H -5.913182 0.783800 1.989642 H -6.801425 -0.632499 1.361182 C -3.886509 1.724228 0.245358 H -4.756571 2.263412 0.603538 C -2.745153 2.448752 -0.123774 H -2.754709 3.531461 -0.022258 C -1.600483 1.796657 -0.589110 C -0.292456 2.522128 -0.886526 H -0.319206 2.986829 -1.881212 C 0.947427 1.604235 -0.781276 H 1.136731 1.107419 -1.742504 H 0.762935 0.797360 -0.064962 C 2.225468 2.300532 -0.326648 C 3.371825 1.518001 0.201978 H 4.001513 2.168843 0.800355 C 3.774024 0.228692 0.055765 O 4.857703 -0.269821 0.716437 C 5.531266 0.526144 1.684653 H 6.018217 1.391789 1.219688 H 6.288777 -0.124497 2.124861 H 4.840753 0.873816 2.462052 C 3.292316 -0.843075 -0.895871 H 4.133672 -1.004243 -1.583157 H 2.462459 -0.476433 -1.499291 C 2.922588 -2.226825 -0.255023 H 3.320148 -3.014513 -0.904572 H 3.436363 -2.325875 0.705846 O 2.292947 3.524305 -0.281697 H -0.173112 3.354756 -0.185193 C -1.660823 0.404291 -0.685932 H -0.807020 -0.134715 -1.065663 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.31116141 Predicted Change= 3.226889D-07 Zero-point correction (ZPE)= -1113.9218 0.38926 Internal Energy (U)= -1113.8994 0.41168 Enthalpy (H)= -1113.8985 0.41262 Gibbs Free Energy (G)= -1113.9753 0.33581 ------------------------------------------------------------------------------ Frequencies -- 4.4453 31.9333 37.3467

5.7.11 TSb→bca Supporting Information: E-Garugamblin-b-CO-pAnsa-mAnsa-idenCO-mAnsa-pAnsa-d3-TS-.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.29547745 Predicted Change= -3.667560D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00122 || 0.00180 [ YES ] 0.00122 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.838583 -2.808307 1.360081 H 1.542788 -2.904117 2.184221 C -0.485721 -2.463947 1.642859 H -0.822413 -2.323910 2.665510 C -1.333753 -2.130153 0.588695 O -2.513876 -1.440266 0.841772


S113

S113

C -2.460037 -0.099984 0.453906 C -0.952789 -2.395995 -0.728814 H -1.659137 -2.210981 -1.532506 C 0.369249 -2.744801 -0.994868 H 0.703366 -2.805739 -2.029248 C 1.314168 -2.823478 0.041194 C -3.508731 0.380221 -0.355476 O -4.464238 -0.526905 -0.709903 C -5.555608 -0.067814 -1.488208 H -5.227149 0.314056 -2.464743 H -6.121070 0.717522 -0.968704 H -6.199961 -0.935909 -1.639681 C -3.489952 1.722983 -0.742452 H -4.282616 2.123261 -1.364653 C -2.446641 2.562897 -0.340209 H -2.465083 3.604033 -0.654775 C -1.399510 2.102876 0.463165 C -0.312978 3.067633 0.926943 H -0.697760 4.086632 0.804012 C 1.053266 2.990090 0.202070 H 1.584364 3.948697 0.311776 H 0.923199 2.847985 -0.878781 C 1.974368 1.889176 0.737753 C 3.197605 1.565701 -0.051725 H 3.760062 2.404910 -0.450982 C 3.502644 0.287264 -0.401961 O 4.570116 -0.098682 -1.133375 C 5.545836 0.883068 -1.469637 H 5.127592 1.634460 -2.151133 H 6.354458 0.346477 -1.968050 H 5.924432 1.381125 -0.569264 C 2.493232 -0.804686 -0.158135 H 1.680843 -0.595694 -0.865593 H 2.070158 -0.607021 0.823273 C 2.733459 -2.337470 -0.237186 H 3.101863 -2.645074 -1.221660 H 3.451008 -2.673770 0.519598 O 1.676597 1.296683 1.768891 H -0.127929 2.924945 1.996615 C -1.431356 0.751549 0.856459 H -0.641818 0.360530 1.488971 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.29547745 Predicted Change= -3.667560D-09 Zero-point correction (ZPE)= -1113.9070 0.38838 Internal Energy (U)= -1113.8855 0.40994 Enthalpy (H)= -1113.8845 0.41088 Gibbs Free Energy (G)= -1113.9574 0.33801 ------------------------------------------------------------------------------ Frequencies -- -123.6861 15.4302 42.4546

5.7.12 TSc→ca Supporting Information: E-Garugamblin-c-pAnsa-mAnsa-CO-idenpAnsa-CO-mAnsa-f2-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.30918834 Predicted Change= -6.386387D-11 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00034 || 0.00180 [ YES ] 0.00034 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -0.686301 -2.739244 -1.342693 H -1.176665 -3.048689 -2.263198 C 0.707312 -2.643857 -1.314935 H 1.303072 -2.844786 -2.200172 C 1.328346 -2.157141 -0.167661 O 2.654529 -1.728215 -0.227499 C 2.731198 -0.338294 -0.260228

C 0.585750 -1.930761 0.993419 H 1.094264 -1.586027 1.888589 C -0.803750 -2.028333 0.950297 H -1.384044 -1.785045 1.837306 C -1.466787 -2.356723 -0.241718 C 3.878091 0.299529 0.256380 O 4.889065 -0.516553 0.670963 C 6.055098 0.090415 1.200215 H 5.833704 0.675690 2.103214 H 6.543082 0.741165 0.462109 H 6.727526 -0.729868 1.458188 C 3.878741 1.696986 0.327149 H 4.742506 2.213744 0.730573 C 2.757165 2.448612 -0.060110 H 2.773793 3.527627 0.073078 C 1.631907 1.821635 -0.590442 C 0.313342 2.507067 -0.908505 H 0.379888 3.587092 -0.741156 C -0.816729 1.904417 -0.045457 H -0.701269 2.219376 1.003591 H -0.738071 0.812399 0.001601 C -2.242359 2.241371 -0.445584 C -3.324073 1.531238 0.331152 H -3.839141 2.190546 1.024961 C -3.741757 0.256616 0.199919 O -4.736774 -0.296252 0.959981 C -5.303346 0.471618 2.010125 H -4.534702 0.800938 2.721195 H -6.014135 -0.185681 2.514263 H -5.832551 1.350764 1.620187 C -3.341987 -0.731167 -0.873606 H -2.538944 -0.309687 -1.485325 H -4.217491 -0.816468 -1.531505 C -2.960546 -2.170862 -0.392060 H -3.485108 -2.382226 0.544717 H -3.339957 -2.884134 -1.132265 O -2.508771 3.107261 -1.260862 H 0.055210 2.377802 -1.967594 C 1.677745 0.430361 -0.732809 H 0.822276 -0.075358 -1.160103 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.30918834 Predicted Change= -6.386387D-11 Zero-point correction (ZPE)= -1113.9208 0.38834 Internal Energy (U)= -1113.8992 0.40996 Enthalpy (H)= -1113.8982 0.41091 Gibbs Free Energy (G)= -1113.9710 0.33811 ------------------------------------------------------------------------------ Frequencies -- -55.9764 26.4847 38.5398

5.7.13 TSc→cb Supporting Information: E-Garugamblin-c-pAnsa-CO-mAnsa-f-QST2TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,qst2,calcfc) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.30665393 Predicted Change= -9.018198D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00159 || 0.00180 [ YES ] 0.00159 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -0.412180 -2.390454 -0.977611 H -0.744264 -2.422428 -2.013522 C 0.940000 -2.198997 -0.714087 H 1.656948 -2.065259 -1.518522 C 1.363550 -2.052309 0.607404 O 2.629818 -1.516433 0.861320 C 2.648310 -0.150225 0.565598 C 0.480382 -2.303297 1.654291 H 0.833260 -2.235776 2.679175 C -0.878178 -2.474655 1.371497


S114

S114

H -1.582937 -2.536396 2.197682 C -1.357474 -2.412880 0.060029 C 3.669791 0.364902 -0.255647 O 4.631181 -0.515728 -0.660084 C 5.674753 -0.023384 -1.481252 H 6.252564 0.762068 -0.975310 H 5.291672 0.371616 -2.432383 H 6.325628 -0.876753 -1.681530 C 3.611350 1.717634 -0.612900 H 4.382934 2.146072 -1.242995 C 2.543917 2.525877 -0.198397 H 2.516541 3.563600 -0.524866 C 1.528914 2.020204 0.616884 C 0.336754 2.861657 1.053548 H 0.072765 2.604215 2.086555 C -0.953776 2.774526 0.192371 H -0.708030 2.930267 -0.869139 H -1.623748 3.603349 0.461281 C -1.727992 1.456969 0.281709 C -3.148764 1.426804 -0.108110 H -3.731097 2.329831 0.045545 C -3.743070 0.301263 -0.593801 O -5.081172 0.186672 -0.785939 C -5.940868 1.217057 -0.311058 H -5.770092 1.411883 0.754288 H -6.957641 0.852496 -0.465777 H -5.796143 2.145305 -0.877642 C -3.043583 -0.917663 -1.157114 H -2.072067 -0.596632 -1.532547 H -3.648493 -1.207564 -2.023711 C -2.828203 -2.184983 -0.248569 H -3.390669 -2.086198 0.685384 H -3.253529 -3.049088 -0.775129 O -1.175894 0.435637 0.672552 H 0.637374 3.916977 1.065903 C 1.638699 0.684641 1.023671 H 0.863571 0.261115 1.643726 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.30665393 Predicted Change= -9.018198D-09 Zero-point correction (ZPE)= -1113.9180 0.38865 Internal Energy (U)= -1113.8966 0.41002 Enthalpy (H)= -1113.8956 0.41097 Gibbs Free Energy (G)= -1113.9675 0.33913 ------------------------------------------------------------------------------ Frequencies -- -44.3411 21.8803 43.1157

5.7.14 Intab Supporting Information: E-Garugamblin-a-mAnsa-CO-pAnsa-e-GS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.31753014 Predicted Change= -1.125523D-07 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.01948 || 0.00180 [ NO ] 0.01948 || 0.00180 [ NO ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.315641 -1.878832 0.896466 H 1.953199 -1.530732 1.704540 C -0.065158 -1.888611 1.071075 H -0.517296 -1.522981 1.987771 C -0.887798 -2.248561 0.002715 O -2.239305 -1.920330 0.047675 C -2.442805 -0.560166 -0.179712 C -0.338717 -2.768784 -1.167014 H -0.996440 -3.078802 -1.973401 C 1.048323 -2.741131 -1.333050 H 1.475767 -3.061320 -2.280978 C 1.887121 -2.217551 -0.339782 C -3.610864 0.036307 0.331882

O -4.480020 -0.791020 0.982141 C -5.653713 -0.217126 1.529811 H -6.284565 0.235994 0.752918 H -5.418122 0.542570 2.287600 H -6.196699 -1.039335 1.999922 C -3.776845 1.414646 0.156465 H -4.657172 1.906125 0.555657 C -2.804049 2.186784 -0.492158 H -2.951197 3.260814 -0.572273 C -1.654275 1.597653 -1.018532 C -0.584122 2.394902 -1.750545 H -0.774554 2.353104 -2.832841 C 0.865344 1.920224 -1.514382 H 1.532084 2.447873 -2.213398 H 0.976011 0.859631 -1.751179 C 1.375483 2.227382 -0.105137 C 2.554664 1.586294 0.523818 H 2.732041 2.085972 1.470432 C 3.400509 0.571282 0.209497 O 4.421943 0.212594 1.041620 C 4.638397 0.907638 2.264557 H 4.847683 1.969034 2.087011 H 5.509013 0.432541 2.719822 H 3.775899 0.816458 2.935430 C 3.472564 -0.339001 -0.993755 H 4.465320 -0.191363 -1.439540 H 2.735006 -0.055288 -1.744654 C 3.321246 -1.856433 -0.650725 H 3.672185 -2.428786 -1.516977 H 3.989099 -2.091773 0.183892 O 0.817424 3.107304 0.544475 H -0.656676 3.445646 -1.456203 C -1.515808 0.215053 -0.868286 H -0.641750 -0.275573 -1.270089 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.31753014 Predicted Change= -1.125523D-07 Zero-point correction (ZPE)= -1113.9275 0.38995 Internal Energy (U)= -1113.9055 0.41196 Enthalpy (H)= -1113.9046 0.41291 Gibbs Free Energy (G)= -1113.9789 0.33854 ------------------------------------------------------------------------------ Frequencies -- 13.5998 31.2716 48.8331

5.7.15 Intba Supporting Information: E-Garugamblin-b-CO-mAnsa-pAnsa-e-GS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.31744263 Predicted Change= -3.265231D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00111 || 0.00180 [ YES ] 0.00111 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.506012 -2.031243 -0.795970 H -2.280318 -1.853570 -1.537738 C -0.166604 -2.008611 -1.187472 H 0.116309 -1.785686 -2.211548 C 0.825495 -2.136172 -0.218032 O 2.130355 -1.766622 -0.520697 C 2.404710 -0.447977 -0.170338 C 0.493732 -2.461471 1.097420 H 1.285764 -2.592494 1.828275 C -0.847053 -2.471476 1.475914 H -1.105281 -2.641084 2.519161 C -1.860472 -2.172847 0.553142 C 3.736299 -0.006443 -0.280989 O 4.640973 -0.918950 -0.743349 C 5.987008 -0.501796 -0.883562 H 6.422465 -0.202214 0.079752


S115

S115

H 6.081776 0.331314 -1.593402 H 6.529267 -1.367221 -1.269481 C 4.027568 1.311197 0.088876 H 5.044756 1.679124 0.013029 C 3.029444 2.167727 0.568236 H 3.300098 3.180405 0.858198 C 1.705852 1.736886 0.679221 C 0.621944 2.639105 1.257916 H 0.876568 2.860312 2.303742 C -0.815541 2.086798 1.230167 H -1.441562 2.697300 1.898111 H -0.856141 1.072904 1.638383 C -1.464409 2.168869 -0.156008 C -2.712478 1.473787 -0.551611 H -3.008000 1.861148 -1.520969 C -3.503939 0.505018 -0.023776 O -4.622181 0.066553 -0.672794 C -5.005312 0.635099 -1.920062 H -5.195851 1.710441 -1.824697 H -5.925808 0.122248 -2.203904 H -4.239777 0.469797 -2.687424 C -3.400342 -0.282868 1.259494 H -4.331832 -0.110650 1.814781 H -2.579795 0.082596 1.877939 C -3.248685 -1.822281 1.034867 H -3.453398 -2.318729 1.990427 H -4.017881 -2.148539 0.328257 O -0.972392 2.922897 -0.990839 H 0.626476 3.595916 0.725780 C 1.421079 0.427476 0.285348 H 0.404419 0.072989 0.338069 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.31744263 Predicted Change= -3.265231D-09 Zero-point correction (ZPE)= -1113.9276 0.38978 Internal Energy (U)= -1113.9055 0.41186 Enthalpy (H)= -1113.9046 0.41281 Gibbs Free Energy (G)= -1113.9794 0.33803 ------------------------------------------------------------------------------ Frequencies -- 11.8452 28.0983 52.1248

5.7.16 Intca Supporting Information: E-Garugamblin-c-pAnsa-mAnsa-CO-idenpAnsa-CO-mAnsa-g-GS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.33181920 Predicted Change= -1.315052D-08 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00102 || 0.00180 [ YES ] 0.00102 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.141023 -2.120793 -1.414917 H -1.484283 -2.036101 -2.442572 C 0.223362 -2.088206 -1.150371 H 0.947430 -1.971156 -1.950419 C 0.662224 -2.093976 0.173899 O 1.993563 -1.797080 0.449192 C 2.288851 -0.447317 0.347973 C -0.237136 -2.274664 1.220307 H 0.130536 -2.304592 2.241550 C -1.605885 -2.303021 0.938909 H -2.317404 -2.370277 1.758808 C -2.077203 -2.157576 -0.371201 C 3.648784 -0.093432 0.209907 O 4.538914 -1.126798 0.199401 C 5.913006 -0.814412 0.054245 H 6.275507 -0.186796 0.879852 H 6.114867 -0.305275 -0.898130 H 6.439623 -1.770506 0.070426

C 3.975853 1.258486 0.089278 H 5.011919 1.556774 -0.025222 C 2.978902 2.243864 0.101176 H 3.267763 3.286869 -0.004369 C 1.636031 1.902451 0.249969 C 0.535953 2.946691 0.283903 H -0.044022 2.839685 1.210996 C -0.428995 2.948494 -0.931699 H 0.143779 3.006351 -1.861635 H -1.042884 3.860205 -0.865151 C -1.408700 1.774561 -1.102192 C -2.315963 1.511089 0.031633 H -2.158541 2.141082 0.900087 C -3.315312 0.587137 0.082379 O -4.101635 0.405683 1.172207 C -3.873349 1.174914 2.348709 H -2.860871 1.012188 2.736326 H -4.607824 0.827228 3.076808 H -4.023441 2.244187 2.157487 C -3.744242 -0.360386 -1.007974 H -3.196279 -0.107394 -1.915246 H -4.815482 -0.194653 -1.185564 C -3.533534 -1.861365 -0.648973 H -4.148250 -2.117859 0.220124 H -3.903101 -2.455358 -1.494263 O -1.428243 1.166343 -2.168962 H 0.996088 3.940912 0.334736 C 1.314360 0.544446 0.383551 H 0.278185 0.257397 0.509592 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.33181920 Predicted Change= -1.315052D-08 Zero-point correction (ZPE)= -1113.9420 0.38976 Internal Energy (U)= -1113.9199 0.41182 Enthalpy (H)= -1113.9190 0.41276 Gibbs Free Energy (G)= -1113.9928 0.33895 ------------------------------------------------------------------------------ Frequencies -- 22.8318 36.4107 68.5598

5.7.17 Intcb Supporting Information: E-Garugamblin-c-pAnsa-CO-mAnsa-g-GS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.33181903 Predicted Change= -5.622017D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00838 || 0.00180 [ NO ] 0.00838 || 0.00180 [ NO ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.142316 -2.121835 -1.414709 H -1.486373 -2.037838 -2.442150 C 0.222292 -2.089283 -1.151265 H 0.945766 -1.972928 -1.951962 C 0.662190 -2.094097 0.172650 O 1.993822 -1.797240 0.446542 C 2.288907 -0.447392 0.346259 C -0.236365 -2.273760 1.219925 H 0.132106 -2.302923 2.240901 C -1.605325 -2.302134 0.939636 H -2.316220 -2.368633 1.760131 C -2.077656 -2.157641 -0.370233 C 3.649016 -0.093380 0.209937 O 4.539171 -1.126730 0.199997 C 5.913416 -0.814267 0.056558 H 6.274936 -0.186899 0.882779 H 6.116385 -0.304830 -0.895424 H 6.440041 -1.770351 0.073053 C 3.976185 1.258573 0.090296 H 5.012381 1.556927 -0.022869 C 2.979195 2.243943 0.101588


S116

S116

H 3.268164 3.287009 -0.003000 C 1.636179 1.902422 0.248633 C 0.536107 2.946710 0.282208 H -0.043655 2.840349 1.209526 C -0.429074 2.947793 -0.933192 H 0.143507 3.004776 -1.863308 H -1.042694 3.859756 -0.867315 C -1.409338 1.774214 -1.102793 C -2.315979 1.511271 0.031624 H -2.158012 2.141568 0.899763 C -3.315307 0.587361 0.083315 O -4.101004 0.406418 1.173697 C -3.871514 1.175658 2.349952 H -2.858577 1.013066 2.736433 H -4.605130 0.827852 3.078864 H -4.021981 2.244913 2.158927 C -3.745001 -0.360520 -1.006416 H -3.197602 -0.107898 -1.914140 H -4.816329 -0.194724 -1.183390 C -3.534181 -1.861382 -0.647024 H -4.148250 -2.117480 0.222637 H -3.904439 -2.455658 -1.491812 O -1.429865 1.165852 -2.169478 H 0.996282 3.940941 0.332301 C 1.314346 0.544307 0.381076 H 0.278041 0.257236 0.505858 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.33181903 Predicted Change= -5.622017D-08 Zero-point correction (ZPE)= -1113.9420 0.38977 Internal Energy (U)= -1113.9199 0.41182 Enthalpy (H)= -1113.9190 0.41277 Gibbs Free Energy (G)= -1113.9928 0.33896 ------------------------------------------------------------------------------ Frequencies -- 22.9121 36.4309 68.5500

5.7.18 TSab→abc Supporting Information: E-Garugamblin-a-mAnsa-CO-pAnsa-f2-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.29533731 Predicted Change= -7.206580D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00089 || 0.00180 [ YES ] 0.00089 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -0.035818 -2.662787 -1.061890 H -0.366226 -2.652872 -2.098940 C 1.285958 -2.340781 -0.767343 H 1.991494 -2.085587 -1.552100 C 1.661612 -2.171943 0.567013 O 2.802815 -1.430270 0.866396 C 2.588766 -0.078883 0.567389 C 0.813662 -2.586884 1.592169 H 1.149474 -2.525256 2.623132 C -0.512871 -2.899880 1.281446 H -1.218322 -3.071262 2.092354 C -0.982472 -2.812407 -0.036265 C 3.486049 0.564914 -0.304797 O 4.524635 -0.186492 -0.770650 C 5.459136 0.438231 -1.634586 H 5.952654 1.290403 -1.148431 H 4.986305 0.780746 -2.565158 H 6.204223 -0.324418 -1.868632 C 3.231567 1.896620 -0.650581 H 3.895885 2.418785 -1.330036 C 2.101950 2.559860 -0.159751 H 1.921027 3.586160 -0.469025 C 1.208673 1.935565 0.715130

C 0.032159 2.699539 1.309171 H 0.284683 2.956627 2.347329 C -1.342677 1.993189 1.326214 H -1.920750 2.382560 2.178730 H -1.244119 0.925306 1.521059 C -2.259834 2.291886 0.125959 C -3.429952 1.426482 -0.203265 H -4.283731 2.023488 -0.508865 C -3.485772 0.079613 -0.365004 O -4.591366 -0.598598 -0.758198 C -5.810518 0.115208 -0.936634 H -6.091449 0.647931 -0.020409 H -6.563641 -0.637209 -1.175713 H -5.730322 0.832278 -1.762533 C -2.286357 -0.826571 -0.253639 H -1.770793 -0.589693 0.677044 H -1.583072 -0.535816 -1.042700 C -2.414400 -2.375475 -0.297736 H -3.104102 -2.735411 0.473320 H -2.792245 -2.710283 -1.269365 O -2.143711 3.360498 -0.461131 H -0.089958 3.648330 0.777524 C 1.491263 0.610210 1.078809 H 0.833269 0.079857 1.759236 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.29533731 Predicted Change= -7.206580D-09 Zero-point correction (ZPE)= -1113.9068 0.38852 Internal Energy (U)= -1113.8852 0.41010 Enthalpy (H)= -1113.8842 0.41105 Gibbs Free Energy (G)= -1113.9574 0.33792 ------------------------------------------------------------------------------ Frequencies -- -135.4241 18.9791 41.4998

5.7.19 TSba→bac Supporting Information: E-Garugamblin-b-CO-mAnsa-pAnsa-f2-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) gfinput opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.29547749 Predicted Change= 4.276611D-09 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00255 || 0.00180 [ NO ] 0.00255 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.838076 -2.808349 1.360277 H 1.542455 -2.904229 2.184259 C -0.486123 -2.463831 1.643351 H -0.822565 -2.323730 2.666076 C -1.334346 -2.129947 0.589372 O -2.514256 -1.439762 0.842663 C -2.460055 -0.099589 0.454450 C -0.953724 -2.395873 -0.728216 H -1.660236 -2.210773 -1.531746 C 0.368219 -2.744798 -0.994566 H 0.702097 -2.805755 -2.029025 C 1.313366 -2.823559 0.041281 C -3.508207 0.380550 -0.355663 O -4.463675 -0.526513 -0.710359 C -5.554461 -0.067485 -1.489522 H -5.225295 0.314013 -2.465964 H -6.120125 0.718115 -0.970639 H -6.198865 -0.935518 -1.641134 C -3.488950 1.723180 -0.743075 H -4.281197 2.123415 -1.365834 C -2.445679 2.563004 -0.340563 H -2.463735 3.604036 -0.655498 C -1.399065 2.103040 0.463525 C -0.312545 3.067722 0.927473 H -0.697297 4.086751 0.804695


S117

S117

C 1.053681 2.990205 0.202565 H 1.584914 3.948701 0.312597 H 0.923570 2.848478 -0.878328 C 1.974725 1.889036 0.737867 C 3.197716 1.565305 -0.051905 H 3.760416 2.404424 -0.451019 C 3.502354 0.286838 -0.402398 O 4.569710 -0.099338 -1.133877 C 5.545838 0.882116 -1.469817 H 5.127968 1.633784 -2.151240 H 6.354339 0.345323 -1.968212 H 5.924483 1.379874 -0.569300 C 2.492482 -0.804789 -0.159171 H 1.680810 -0.595930 -0.867495 H 2.068527 -0.606742 0.821770 C 2.732626 -2.337635 -0.237384 H 3.101126 -2.645756 -1.221663 H 3.450108 -2.673503 0.519656 O 1.677119 1.296520 1.769036 H -0.127483 2.924861 1.997116 C -1.431416 0.751866 0.857275 H -0.642271 0.360866 1.490289 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.29547749 Predicted Change= 4.276611D-09 Zero-point correction (ZPE)= -1113.9070 0.38838 Internal Energy (U)= -1113.8855 0.40994 Enthalpy (H)= -1113.8845 0.41088 Gibbs Free Energy (G)= -1113.9574 0.33801 ------------------------------------------------------------------------------ Frequencies -- -123.7429 15.4102 42.4416

5.7.20 TSca→cab Supporting Information: E-Garugamblin-c-pAnsa-mAnsa-CO-idenpAnsa-CO-mAnsa-h-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.31832986 Predicted Change= -3.956541D-11 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00007 || 0.00180 [ YES ] 0.00007 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.739080 -2.170150 1.342519 H 0.854859 -2.178034 2.423837 C -0.531110 -2.051656 0.795876 H -1.407881 -1.961383 1.428969 C -0.671087 -1.931860 -0.588430 O -1.898882 -1.554527 -1.122240 C -2.290221 -0.295043 -0.680049 C 0.426662 -2.091780 -1.428422 H 0.288624 -2.035871 -2.504039 C 1.699046 -2.214054 -0.862308 H 2.569407 -2.259961 -1.513267 C 1.878102 -2.179189 0.525160 C -3.602512 -0.136491 -0.197261 O -4.399908 -1.242860 -0.232809 C -5.722613 -1.119046 0.259616 H -6.300338 -0.379252 -0.311062 H -5.736091 -0.841117 1.322463 H -6.179212 -2.103287 0.138961 C -3.974258 1.114520 0.303446 H -4.971281 1.270201 0.700075 C -3.056051 2.168416 0.333434 H -3.370958 3.122822 0.748669 C -1.757125 2.025748 -0.162973 C -0.845641 3.239424 -0.231174 H -0.905415 3.635091 -1.254562 C 0.683879 3.158688 0.118495

H 0.872910 3.874825 0.928566 H 1.255714 3.523842 -0.739911 C 1.319730 1.852940 0.631237 C 2.512117 1.415564 -0.124401 H 2.690857 1.964565 -1.041593 C 3.407126 0.448763 0.218066 O 4.481324 0.134234 -0.548826 C 4.689488 0.797169 -1.791482 H 3.843384 0.638994 -2.470420 H 5.591228 0.352979 -2.215889 H 4.843396 1.873051 -1.645494 C 3.410358 -0.411938 1.452928 H 2.612394 -0.072773 2.114300 H 4.377018 -0.267182 1.954346 C 3.235316 -1.928860 1.137922 H 4.039059 -2.256494 0.470372 H 3.348330 -2.478508 2.080306 O 0.878946 1.306436 1.636714 H -1.294010 4.015267 0.397824 C -1.402074 0.777016 -0.685855 H -0.403100 0.606872 -1.073219 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.31832986 Predicted Change= -3.956541D-11 Zero-point correction (ZPE)= -1113.9288 0.38946 Internal Energy (U)= -1113.9073 0.41094 Enthalpy (H)= -1113.9064 0.41188 Gibbs Free Energy (G)= -1113.9790 0.33927 ------------------------------------------------------------------------------ Frequencies -- -168.2625 22.5752 33.5291

5.7.21 TScb→cba Supporting Information: E-Garugamblin-c-pAnsa-CO-mAnsa-h-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.31832984 Predicted Change= -2.843651D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00061 || 0.00180 [ YES ] 0.00061 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.739181 -2.170044 1.342616 H 0.854991 -2.177869 2.423931 C -0.531027 -2.051584 0.796004 H -1.407778 -1.961276 1.429119 C -0.671045 -1.931866 -0.588305 O -1.898857 -1.554577 -1.122109 C -2.290228 -0.295084 -0.679974 C 0.426682 -2.091829 -1.428319 H 0.288611 -2.035978 -2.503936 C 1.699083 -2.214069 -0.862236 H 2.569425 -2.260009 -1.513217 C 1.878180 -2.179132 0.525225 C -3.602555 -0.136526 -0.197285 O -4.399948 -1.242895 -0.232874 C -5.722699 -1.119062 0.259422 H -6.300363 -0.379273 -0.311324 H -5.736277 -0.841115 1.322263 H -6.179296 -2.103302 0.138740 C -3.974337 1.114492 0.303377 H -4.971387 1.270178 0.699937 C -3.056131 2.168388 0.333419 H -3.371065 3.122797 0.748626 C -1.757171 2.025715 -0.162900 C -0.845700 3.239405 -0.231064 H -0.905545 3.635151 -1.254418 C 0.683845 3.158661 0.118513 H 0.872950 3.874814 0.928552 H 1.255633 3.523790 -0.739935 C 1.319742 1.852924 0.631233


S118

S118

C 2.512092 1.415564 -0.124472 H 2.690751 1.964537 -1.041697 C 3.407150 0.448803 0.217970 O 4.481302 0.134270 -0.548985 C 4.689344 0.797141 -1.791695 H 3.843186 0.638908 -2.470551 H 5.591059 0.352949 -2.216155 H 4.843241 1.873035 -1.645780 C 3.410491 -0.411847 1.452867 H 2.612587 -0.072655 2.114298 H 4.377196 -0.267074 1.954193 C 3.235418 -1.928781 1.137932 H 4.039133 -2.256449 0.470365 H 3.348462 -2.478392 2.080334 O 0.879034 1.306418 1.636741 H -1.294046 4.015194 0.398014 C -1.402086 0.776978 -0.685746 H -0.403091 0.606830 -1.073052 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.31832984 Predicted Change= -2.843651D-10 Zero-point correction (ZPE)= -1113.9288 0.38946 Internal Energy (U)= -1113.9073 0.41094 Enthalpy (H)= -1113.9064 0.41188 Gibbs Free Energy (G)= -1113.9790 0.33927 ------------------------------------------------------------------------------ Frequencies -- -168.2672 22.5715 33.5268

5.7.22 ent- C9-E-Garugamblin I Supporting Information: E-Garugamblin-a-mAnsa-CO-pAnsa-i-GS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevB.01 12-Aug-2010 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.33555300 Predicted Change= -2.507184D-08 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00350 || 0.00180 [ NO ] 0.00350 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.248366 -2.424723 -1.460146 H -1.721333 -2.604850 -2.422862 C 0.144131 -2.405444 -1.378436 H 0.762849 -2.556682 -2.257505 C 0.747423 -2.080597 -0.165759 O 2.112806 -1.821764 -0.120040 C 2.423903 -0.469821 -0.151797 C -0.020023 -1.914781 0.986658 H 0.475960 -1.696600 1.927523 C -1.409291 -1.945316 0.890987 H -2.010861 -1.764507 1.778843 C -2.044085 -2.131839 -0.344913 C 3.697093 -0.088704 0.323273 O 4.506069 -1.099727 0.755844 C 5.796518 -0.756364 1.227148 H 5.746739 -0.097416 2.105119 H 6.396409 -0.267577 0.447301 H 6.271604 -1.697683 1.510239 C 4.025304 1.268392 0.325178 H 4.993959 1.590749 0.690540 C 3.109179 2.231236 -0.122084 H 3.391366 3.281020 -0.089417 C 1.855801 1.859856 -0.605696 C 0.835078 2.877958 -1.082550 H 1.286371 3.875936 -1.044735 C -0.474495 2.898417 -0.265144 H -0.976334 3.868791 -0.408131 H -0.261568 2.825008 0.808247 C -1.512078 1.834167 -0.667344 C -2.511457 1.523904 0.368985 H -2.414483 2.106450 1.278696

C -3.487001 0.576848 0.308356 O -4.344084 0.333095 1.331429 C -4.252133 1.091831 2.533037 H -3.276811 0.954258 3.014738 H -5.040829 0.711467 3.183907 H -4.415552 2.158649 2.339902 C -3.793614 -0.357253 -0.832594 H -3.210555 -0.051806 -1.701371 H -4.861000 -0.245111 -1.065092 C -3.521989 -1.857157 -0.500730 H -4.070689 -2.128889 0.407665 H -3.937217 -2.454742 -1.320687 O -1.485502 1.336768 -1.790807 H 0.569157 2.684661 -2.128756 C 1.540841 0.492775 -0.626824 H 0.584076 0.181591 -1.023217 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.33555300 Predicted Change= -2.507184D-08 Zero-point correction (ZPE)= -1113.9458 0.38973 Internal Energy (U)= -1113.9237 0.41183 Enthalpy (H)= -1113.9227 0.41278 Gibbs Free Energy (G)= -1113.9968 0.33873 ------------------------------------------------------------------------------ Frequencies -- 23.0924 32.1063 62.8959


5.8.1 C11-E-Garugamblin I Supporting Information: a-000-E-Garugamblin-1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.33019525 Predicted Change= -6.981268D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00116 || 0.00180 [ YES ] 0.00116 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.686262 -2.195939 1.304761 H 2.226732 -2.051489 2.237921 C 0.293352 -2.154260 1.313841 H -0.261078 -1.970330 2.229051 C -0.398938 -2.267061 0.108931 O -1.762518 -2.003931 0.082121 C -2.096349 -0.682462 -0.168769 C 0.278132 -2.553340 -1.073869 H -0.283297 -2.665420 -1.996349 C 1.672742 -2.568079 -1.070889 H 2.205883 -2.690489 -2.009619 C 2.397142 -2.326479 0.102661 C -3.446479 -0.329783 0.031651 O -4.273928 -1.330993 0.452721 C -5.639729 -1.017094 0.655291 H -6.117879 -0.668104 -0.270239 H -5.770429 -0.253794 1.434901 H -6.114918 -1.945534 0.977991 C -3.829720 0.993137 -0.200609 H -4.859690 1.294196 -0.044399 C -2.897651 1.945238 -0.627219 H -3.230101 2.966558 -0.798799 C -1.561770 1.602289 -0.842729 C -0.586561 2.639349 -1.382949 H -0.804711 2.799409 -2.448729 C 0.920889 2.323210 -1.295409 H 1.458349 3.132791 -1.810719 H 1.190020 1.417031 -1.840509 C 1.492089 2.230621 0.098611 C 2.509020 1.418021 0.505991 H 2.801180 1.443162 1.549341


S119

S119

C 3.233580 0.447012 -0.322989 O 3.148761 0.363932 -1.547459 C 4.148521 -0.534898 0.431581 H 4.034881 -0.410888 1.514121 H 5.190001 -0.284347 0.187481 C 3.877612 -2.011588 0.036911 H 4.237932 -2.176787 -0.982539 H 4.464383 -2.660527 0.700161 O 0.865689 3.095950 0.925581 H -0.783502 3.598539 -0.892259 C -1.180269 0.276039 -0.601079 H -0.151489 -0.020260 -0.751659 C 1.251479 3.181831 2.293271 H 0.603808 3.940440 2.735041 H 2.299978 3.487511 2.389931 H 1.099779 2.224080 2.804201 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.33019525 Predicted Change= -6.981268D-09 Zero-point correction (ZPE)= -1113.9406 0.38955 Internal Energy (U)= -1113.9184 0.41170 Enthalpy (H)= -1113.9175 0.41264 Gibbs Free Energy (G)= -1113.9920 0.33811 ------------------------------------------------------------------------------ Frequencies -- 15.4781 31.3897 51.7590

5.8.2 TSa Supporting Information: a-005-mAnsa-pCO-E-Garugamblin-1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.32135908 Predicted Change= -1.663131D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00089 || 0.00180 [ YES ] 0.00089 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.865790 -2.068383 1.226742 H 2.339918 -1.885612 2.188827 C 0.479271 -2.189045 1.165349 H -0.136856 -2.092099 2.054379 C -0.137264 -2.336825 -0.076777 O -1.512172 -2.154203 -0.175020 C -1.881494 -0.831790 -0.391142 C 0.625343 -2.538295 -1.224221 H 0.127058 -2.692243 -2.176496 C 2.010539 -2.383117 -1.151506 H 2.597713 -2.421693 -2.065300 C 2.640759 -2.063816 0.056914 C -3.214451 -0.482387 -0.082490 O -4.001297 -1.486853 0.402264 C -5.353816 -1.184269 0.694176 H -5.893936 -0.840862 -0.198558 H -5.439289 -0.420530 1.479586 H -5.798555 -2.116139 1.048649 C -3.622146 0.837939 -0.285676 H -4.639478 1.131288 -0.051862 C -2.733325 1.798269 -0.788843 H -3.085652 2.815768 -0.939279 C -1.420664 1.458454 -1.108219 C -0.446811 2.433239 -1.743917 H -0.044552 1.959455 -2.646436 C 0.791334 2.936166 -0.905424 H 0.649552 4.001922 -0.691070 H 1.695341 2.818553 -1.501545 C 1.017532 2.281559 0.427126 C 2.015769 1.418538 0.768853 H 2.071578 1.089337 1.799175 C 3.036151 0.846377 -0.120057 O 3.089640 1.014586 -1.337713

C 4.091817 -0.047670 0.560048 H 3.970654 -0.022723 1.648388 H 5.078681 0.375196 0.333763 C 4.055149 -1.520895 0.061472 H 4.456765 -1.556980 -0.955826 H 4.724881 -2.115971 0.696373 O 0.090084 2.721078 1.306966 H -1.001288 3.313972 -2.083742 C -1.015821 0.131355 -0.899650 H -0.001040 -0.143964 -1.154328 C 0.030346 2.162676 2.615821 H -0.843544 2.613172 3.088614 H 0.928792 2.409926 3.194356 H -0.090811 1.074890 2.568886 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.32135908 Predicted Change= -1.663131D-09 Zero-point correction (ZPE)= -1113.9317 0.38963 Internal Energy (U)= -1113.9102 0.41108 Enthalpy (H)= -1113.9093 0.41202 Gibbs Free Energy (G)= -1113.9816 0.33967 ------------------------------------------------------------------------------ Frequencies -- -84.0049 30.7487 35.2176

5.8.3 TSb Supporting Information: b-005-CO-pCO-E-Garugamblin-1-plus1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.31139953 Predicted Change= -8.292579D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00131 || 0.00180 [ YES ] 0.00131 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.325082 3.276060 -0.962095 H 0.892672 3.672568 -1.802103 C -0.949765 2.754024 -1.195771 H -1.375584 2.742009 -2.194806 C -1.627187 2.117742 -0.155253 O -2.738022 1.315489 -0.423791 C -2.447873 -0.047223 -0.386324 C -1.134098 2.195957 1.147135 H -1.702507 1.751837 1.958742 C 0.139167 2.715804 1.362943 H 0.565854 2.670236 2.362793 C 0.933702 3.151429 0.293944 C -3.468553 -0.946676 -0.014932 O -4.694274 -0.403222 0.242775 C -5.740260 -1.279510 0.620191 H -5.508934 -1.810687 1.553923 H -5.956136 -2.016570 -0.165462 H -6.618352 -0.648845 0.772952 C -3.151870 -2.307424 0.073930 H -3.917109 -3.020340 0.360566 C -1.849938 -2.770127 -0.172082 H -1.639972 -3.831807 -0.061459 C -0.840224 -1.885629 -0.551522 C 0.611354 -2.291034 -0.769114 H 0.676915 -3.337279 -1.090182 C 1.500323 -2.098065 0.511239 H 1.488883 -3.021927 1.099951 H 1.064639 -1.298917 1.109422 C 2.954357 -1.759033 0.254240 C 3.485072 -0.510329 0.062296 H 4.557772 -0.379177 -0.027880 C 2.633551 0.674999 -0.048934 O 1.413222 0.560879 -0.101477 C 3.245240 2.078084 -0.195877 H 3.297392 2.259851 -1.279474


S120

S120

H 4.280777 2.100225 0.165699 C 2.439952 3.248515 0.467339 H 2.673631 3.265941 1.538605 H 2.834356 4.183690 0.048504 O 3.705572 -2.883111 0.286615 H 1.025930 -1.682714 -1.578353 C -1.183721 -0.532841 -0.687852 H -0.417481 0.168766 -0.973352 C 5.107606 -2.800149 0.047084 H 5.474778 -3.826948 0.078341 H 5.605880 -2.206934 0.823132 H 5.313095 -2.360702 -0.936044 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.31139953 Predicted Change= -8.292579D-09 Zero-point correction (ZPE)= -1113.9221 0.38921 Internal Energy (U)= -1113.9010 0.41033 Enthalpy (H)= -1113.9001 0.41127 Gibbs Free Energy (G)= -1113.9709 0.34041 ------------------------------------------------------------------------------ Frequencies -- -60.0946 32.2114 46.5260

5.8.4 TSc Supporting Information: c-005-pAnsa-pCO-E-Garugamblin-1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.32536553 Predicted Change= -1.044566D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00027 || 0.00180 [ YES ] 0.00027 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.577751 -1.952913 1.434176 H 2.040141 -1.722292 2.391710 C 0.189044 -1.944375 1.326172 H -0.442736 -1.697859 2.174036 C -0.397329 -2.179217 0.083580 O -1.760588 -1.970894 -0.078351 C -2.123632 -0.642215 -0.234498 C 0.382002 -2.543092 -1.012510 H -0.099627 -2.746688 -1.963792 C 1.771127 -2.544656 -0.889530 H 2.381703 -2.752830 -1.764004 C 2.389463 -2.188955 0.316655 C -3.480300 -0.326295 -0.026241 O -4.298533 -1.367289 0.307327 C -5.670522 -1.087025 0.517968 H -6.143952 -0.674490 -0.383525 H -5.819514 -0.387133 1.351957 H -6.136388 -2.043333 0.763662 C -3.879399 1.006297 -0.161723 H -4.915505 1.280676 0.002488 C -2.954045 2.001037 -0.492903 H -3.296638 3.029764 -0.580016 C -1.609677 1.693674 -0.715324 C -0.633010 2.790977 -1.113652 H -0.904014 3.152647 -2.115648 C 0.863781 2.426118 -1.174502 H 1.395878 3.293944 -1.591953 H 1.064595 1.608420 -1.867772 C 1.528551 2.105109 0.144228 C 2.563506 1.237824 0.338859 H 2.971516 1.134639 1.337925 C 3.192899 0.390017 -0.682326 O 2.884270 0.380220 -1.873176 C 4.325736 -0.533353 -0.202626 H 4.928836 -0.011046 0.549562 H 4.959534 -0.696858 -1.077811 C 3.878517 -1.932392 0.381231

H 4.416326 -2.713080 -0.167615 H 4.209966 -2.003983 1.422627 O 0.994716 2.849523 1.137823 H -0.768871 3.646626 -0.442769 C -1.216555 0.356583 -0.586731 H -0.184479 0.081091 -0.756122 C 1.474765 2.706618 2.470473 H 0.871703 3.384890 3.075813 H 2.532209 2.987951 2.542466 H 1.344379 1.677860 2.825166 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.32536553 Predicted Change= -1.044566D-10 Zero-point correction (ZPE)= -1113.9359 0.38939 Internal Energy (U)= -1113.9144 0.41088 Enthalpy (H)= -1113.9135 0.41182 Gibbs Free Energy (G)= -1113.9862 0.33910 ------------------------------------------------------------------------------ Frequencies -- -75.1556 20.9336 31.5442

5.8.5 Inta Supporting Information: a-010-mAnsa-pCO-E-Garugamblin-1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.32236222 Predicted Change= -1.375320D-08 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00119 || 0.00180 [ YES ] 0.00119 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.858243 -2.014756 1.252467 H 2.395997 -1.747529 2.159428 C 0.470061 -2.129601 1.298125 H -0.082011 -1.935146 2.212983 C -0.231751 -2.379468 0.119471 O -1.601030 -2.133208 0.081068 C -1.901054 -0.823664 -0.281794 C 0.450911 -2.704594 -1.050475 H -0.111419 -2.933070 -1.950706 C 1.838051 -2.552645 -1.088056 H 2.360087 -2.683433 -2.032690 C 2.550209 -2.114948 0.035751 C -3.231532 -0.387674 -0.103868 O -4.099360 -1.303390 0.417575 C -5.450231 -0.913434 0.587488 H -5.916088 -0.637858 -0.368416 H -5.545264 -0.071727 1.287377 H -5.962848 -1.784406 1.000372 C -3.558323 0.922463 -0.467192 H -4.574964 1.277828 -0.340781 C -2.595290 1.791500 -1.000990 H -2.891618 2.799584 -1.281087 C -1.281704 1.365413 -1.184835 C -0.179665 2.203687 -1.803552 H 0.464094 1.542782 -2.391123 C 0.753391 2.993301 -0.830304 H 0.277297 3.942349 -0.562654 H 1.682417 3.203756 -1.365710 C 1.076512 2.311145 0.472801 C 2.068972 1.414330 0.735510 H 2.182773 1.064943 1.754080 C 2.997377 0.827863 -0.235268 O 2.950588 1.018227 -1.450611 C 4.081794 -0.099357 0.350350 H 4.068401 -0.051759 1.444605 H 5.055269 0.286080 0.022643 C 3.962304 -1.580607 -0.110654 H 4.256644 -1.644227 -1.162913 H 4.688181 -2.173656 0.462035 O 0.218669 2.749111 1.422526


S121

S121

H -0.607750 2.934979 -2.499362 C -0.961019 0.052337 -0.813632 H 0.054152 -0.281429 -0.970209 C 0.242669 2.173315 2.725073 H -0.582261 2.638237 3.266879 H 1.187237 2.390685 3.238385 H 0.091202 1.089463 2.673884 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.32236222 Predicted Change= -1.375320D-08 Zero-point correction (ZPE)= -1113.9323 0.39000 Internal Energy (U)= -1113.9102 0.41210 Enthalpy (H)= -1113.9093 0.41304 Gibbs Free Energy (G)= -1113.9830 0.33930 ------------------------------------------------------------------------------ Frequencies -- 29.0861 39.5595 59.4202

5.8.6 Intb Supporting Information: b-010-CO-pCO-E-Garugamblin-1-plus1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.31745780 Predicted Change= -2.287669D-08 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00003 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00163 || 0.00180 [ YES ] 0.00163 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.601195 3.262540 -0.618446 H 1.114033 3.789799 -1.419493 C -0.743937 2.927594 -0.787064 H -1.271768 3.174005 -1.703135 C -1.375836 2.143934 0.176165 O -2.594908 1.534098 -0.114245 C -2.471654 0.157432 -0.282951 C -0.729423 1.856004 1.379393 H -1.251679 1.286874 2.142314 C 0.617452 2.181528 1.524131 H 1.143482 1.873741 2.425534 C 1.326470 2.812229 0.492596 C -3.596666 -0.658045 -0.037147 O -4.755929 -0.011106 0.281104 C -5.903428 -0.799575 0.539370 H -5.754005 -1.464581 1.401267 H -6.185228 -1.404191 -0.333586 H -6.706360 -0.094554 0.763508 C -3.437920 -2.045525 -0.116250 H -4.283838 -2.695708 0.077779 C -2.186483 -2.620638 -0.392113 H -2.091192 -3.704071 -0.385335 C -1.080285 -1.816486 -0.654888 C 0.345137 -2.321286 -0.823148 H 0.370926 -3.413655 -0.906132 C 1.199657 -1.851281 0.395808 H 0.995356 -2.512765 1.245930 H 0.859618 -0.853250 0.672298 C 2.701544 -1.782355 0.250090 C 3.415959 -0.675497 -0.109051 H 4.493240 -0.658716 0.021082 C 2.798500 0.519606 -0.697642 O 1.737711 0.465950 -1.317944 C 3.490935 1.881014 -0.559784 H 3.409914 2.365359 -1.538818 H 4.556851 1.770615 -0.326364 C 2.842426 2.821004 0.515228 H 3.185824 2.512527 1.509497 H 3.243669 3.828438 0.344157 O 3.271998 -2.938394 0.660786 H 0.779887 -1.902554 -1.735387 C -1.266853 -0.426196 -0.646095 H -0.419045 0.206296 -0.871700

C 4.687226 -3.082443 0.587221 H 4.895951 -4.117169 0.863108 H 5.189276 -2.407719 1.291402 H 5.050024 -2.884440 -0.428085 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.31745780 Predicted Change= -2.287669D-08 Zero-point correction (ZPE)= -1113.9277 0.38972 Internal Energy (U)= -1113.9057 0.41173 Enthalpy (H)= -1113.9047 0.41267 Gibbs Free Energy (G)= -1113.9780 0.33945 ------------------------------------------------------------------------------ Frequencies -- 36.1624 41.2881 61.2836

5.8.7 Intc Supporting Information: c-010-pAnsa-pCO-E-Garugamblin-1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.32663661 Predicted Change= -1.053302D-08 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00126 || 0.00180 [ YES ] 0.00126 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.480396 -1.958777 1.490988 H 1.928234 -1.728190 2.455412 C 0.093130 -1.959724 1.366513 H -0.549703 -1.721460 2.208375 C -0.474845 -2.167112 0.110810 O -1.829173 -1.926386 -0.074170 C -2.158657 -0.585504 -0.208779 C 0.320735 -2.519101 -0.977625 H -0.146208 -2.705267 -1.939752 C 1.708581 -2.518227 -0.836159 H 2.326793 -2.712421 -1.708710 C 2.309267 -2.164431 0.380333 C -3.518893 -0.251003 -0.064509 O -4.371488 -1.286002 0.192762 C -5.747624 -0.986394 0.341113 H -6.166600 -0.538791 -0.570540 H -5.927360 -0.308623 1.187156 H -6.241892 -1.940641 0.533473 C -3.887703 1.091893 -0.184195 H -4.927019 1.380064 -0.071876 C -2.930012 2.078548 -0.437734 H -3.251820 3.114629 -0.517302 C -1.579789 1.754644 -0.592550 C -0.564860 2.851285 -0.888300 H -0.860480 3.350052 -1.821502 C 0.910021 2.437188 -1.064430 H 1.452376 3.307039 -1.462999 H 1.033119 1.662223 -1.822322 C 1.645888 2.006784 0.185172 C 2.674497 1.113076 0.248987 H 3.115036 0.892579 1.214890 C 3.218614 0.353719 -0.883325 O 2.928840 0.562392 -2.060196 C 4.231728 -0.762039 -0.566772 H 5.165411 -0.301144 -0.213121 H 4.453789 -1.225676 -1.531835 C 3.787798 -1.841969 0.464161 H 4.406256 -2.734194 0.297418 H 4.014535 -1.504357 1.482188 O 1.172180 2.664181 1.267206 H -0.632614 3.618509 -0.108490 C -1.217152 0.407557 -0.480442 H -0.181718 0.119832 -0.600108 C 1.732675 2.414658 2.551561 H 1.177894 3.049124 3.244326 H 2.796342 2.680085 2.577756


S122

S122

H 1.609990 1.362727 2.833840 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.32663661 Predicted Change= -1.053302D-08 Zero-point correction (ZPE)= -1113.9373 0.38925 Internal Energy (U)= -1113.9151 0.41151 Enthalpy (H)= -1113.9141 0.41246 Gibbs Free Energy (G)= -1113.9888 0.33778 ------------------------------------------------------------------------------ Frequencies -- 18.9988 31.8360 60.3826

5.8.8 TSa→abc Supporting Information: a-015-mAnsa-CO2-pCO-E-Garugamblin-1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.31139955 Predicted Change= -2.315647D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00092 || 0.00180 [ YES ] 0.00092 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -0.139232 2.716165 1.362838 H -0.565886 2.670823 2.362714 C 1.134035 2.196275 1.147107 H 1.702481 1.752360 1.958800 C 1.627098 2.117780 -0.155274 O 2.737980 1.315530 -0.423643 C 2.447903 -0.047196 -0.386205 C 0.949642 2.753847 -1.195904 H 1.375446 2.741650 -2.194943 C -0.325192 3.275939 -0.962306 H -0.892802 3.672270 -1.802385 C -0.933801 3.151556 0.293766 C 3.468655 -0.946612 -0.014926 O 4.694367 -0.403111 0.242725 C 5.740405 -1.279357 0.620095 H 5.956305 -2.016381 -0.165585 H 5.509120 -1.810578 1.553813 H 6.618467 -0.648653 0.772861 C 3.152043 -2.307381 0.073879 H 3.917342 -3.020271 0.360424 C 1.850119 -2.770146 -0.172073 H 1.640222 -3.831843 -0.061488 C 0.840329 -1.885677 -0.551381 C -0.611238 -2.291156 -0.768969 H -1.025813 -1.682958 -1.578303 C -1.500281 -2.098135 0.511335 H -1.064613 -1.298992 1.109529 H -1.488880 -3.021996 1.100054 C -2.954323 -1.759122 0.254308 C -3.485163 -0.510438 0.062512 H -4.557882 -0.379379 -0.027554 C -2.633728 0.674950 -0.048759 O -1.413413 0.560828 -0.101485 C -3.245440 2.078029 -0.195724 H -4.280909 2.100220 0.166035 H -3.297797 2.259614 -1.279346 C -2.440063 3.248620 0.467140 H -2.834481 4.183692 0.048091 H -2.673717 3.266297 1.538406 O -3.705470 -2.883253 0.286539 H -0.676736 -3.337441 -1.089921 C 1.183770 -0.532873 -0.687674 H 0.417508 0.168700 -0.973150 C -5.107487 -2.800367 0.046897 H -5.474579 -3.827200 0.077971 H -5.312918 -2.360791 -0.936185 H -5.605887 -2.207309 0.822985 ------------------------------------------------------------------------------


5.8.9 TSa→ac Supporting Information: a-015-mAnsa-pAnsa-pCO-E-Garugamblin-1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.31868968 Predicted Change= -2.804884D-11 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00005 || 0.00180 [ YES ] 0.00005 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.722300 -2.023666 1.296093 H 2.182631 -1.826832 2.262243 C 0.335858 -2.134659 1.209003 H -0.298667 -2.006407 2.080975 C -0.254573 -2.312851 -0.040836 O -1.622935 -2.105292 -0.177551 C -1.941506 -0.768116 -0.398175 C 0.532671 -2.554639 -1.165494 H 0.053130 -2.733300 -2.123010 C 1.917723 -2.417289 -1.066909 H 2.525759 -2.506252 -1.963735 C 2.523841 -2.065937 0.146852 C -3.264768 -0.357646 -0.132260 O -4.116563 -1.324666 0.318260 C -5.458654 -0.954638 0.578705 H -5.958991 -0.581121 -0.325074 H -5.523906 -0.190282 1.365362 H -5.958792 -1.863893 0.917822 C -3.599864 0.983855 -0.341167 H -4.610404 1.323669 -0.142902 C -2.649554 1.906685 -0.801895 H -2.948998 2.940998 -0.953781 C -1.343842 1.503994 -1.074824 C -0.257190 2.409647 -1.617214 H 0.344236 1.837875 -2.328923 C 0.735737 3.030056 -0.583530 H 0.283258 3.925297 -0.144362 H 1.631616 3.327600 -1.135141 C 1.144284 2.168898 0.586477 C 2.142745 1.243290 0.649388 H 2.362266 0.782866 1.605221 C 2.963422 0.788152 -0.475185 O 2.740362 1.083952 -1.649135 C 4.192586 -0.077103 -0.130579 H 4.704845 0.384403 0.722607 H 4.856105 0.007831 -0.994747 C 3.965161 -1.610931 0.191368 H 4.554961 -2.192187 -0.525178 H 4.383679 -1.825760 1.180665 O 0.384227 2.497967 1.657497 H -0.703058 3.245553 -2.169424 C -1.017864 0.156991 -0.869344 H -0.009984 -0.160487 -1.096073 C 0.518077 1.769898 2.873773 H -0.252323 2.163418 3.538653 H 1.505792 1.927733 3.324417 H 0.356573 0.699641 2.706334 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm


S123

S123


5.8.10 TSb→ba Supporting Information: b-015-CO-mAnsa1-pCO-E-Garugamblin-1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.30889979 Predicted Change= -3.422252D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00032 || 0.00180 [ YES ] 0.00032 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.836662 3.118523 -0.614105 H 1.251914 3.605756 -1.492927 C -0.539641 2.905495 -0.546697 H -1.193913 3.198608 -1.361712 C -1.061079 2.173079 0.517878 O -2.345373 1.648574 0.426094 C -2.351057 0.324588 0.000160 C -0.252653 1.817564 1.596058 H -0.687176 1.279127 2.432726 C 1.122942 2.022664 1.506816 H 1.768067 1.654539 2.301365 C 1.695124 2.596873 0.364102 C -3.577046 -0.371697 0.065310 O -4.647997 0.338890 0.527104 C -5.897710 -0.322533 0.598660 H -5.864222 -1.182188 1.282323 H -6.232859 -0.665607 -0.389865 H -6.605033 0.415235 0.982621 C -3.603449 -1.709938 -0.334102 H -4.533027 -2.266858 -0.293432 C -2.438490 -2.357651 -0.773467 H -2.493469 -3.406023 -1.057765 C -1.227457 -1.672804 -0.845669 C 0.084420 -2.327423 -1.244682 H -0.127378 -3.283811 -1.735819 C 1.003213 -2.616794 -0.019250 H 1.206562 -3.692156 0.027697 H 0.442119 -2.406860 0.902142 C 2.368381 -1.979192 0.218384 C 2.991394 -0.830053 -0.177274 H 3.946848 -0.628671 0.295282 C 2.607920 0.218963 -1.128319 O 1.685882 0.152389 -1.937488 C 3.465696 1.497690 -1.099150 H 3.248622 2.019918 -2.034996 H 4.533685 1.240805 -1.097648 C 3.179897 2.452713 0.103442 H 3.668803 2.067187 1.005787 H 3.653083 3.417615 -0.121301 O 2.971725 -2.802149 1.124733 H 0.605250 -1.694861 -1.964001 C -1.214357 -0.321720 -0.472583 H -0.284304 0.219583 -0.563446 C 4.249745 -2.497517 1.667964 H 4.484237 -3.325204 2.339379 H 4.230611 -1.559340 2.235937 H 5.012956 -2.433428 0.883256 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ==============================================================================

SCF Energy= -1114.30889979 Predicted Change= -3.422252D-10 Zero-point correction (ZPE)= -1113.9195 0.38939 Internal Energy (U)= -1113.8980 0.41081 Enthalpy (H)= -1113.8971 0.41175 Gibbs Free Energy (G)= -1113.9693 0.33957 ------------------------------------------------------------------------------ Frequencies -- -72.4657 24.1009 49.9655

5.8.11 TSb→bc Supporting Information: b-015-CO-pAnsa-pCO-E-Garugamblin-1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.31405511 Predicted Change= 2.404490D-11 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00031 || 0.00180 [ YES ] 0.00031 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.482328 3.282267 -0.828163 H 0.942855 3.762479 -1.688313 C -0.850207 2.876406 -0.911606 H -1.427168 3.024748 -1.819219 C -1.407141 2.156263 0.141688 O -2.620964 1.495573 -0.038514 C -2.469900 0.126402 -0.221879 C -0.698917 1.991104 1.333721 H -1.167234 1.469936 2.163247 C 0.632584 2.397414 1.398517 H 1.204074 2.202312 2.304100 C 1.267940 2.967994 0.286706 C -3.591826 -0.703452 -0.005477 O -4.758133 -0.069613 0.314281 C -5.903548 -0.869656 0.543607 H -5.758598 -1.553158 1.391703 H -6.173782 -1.456065 -0.345357 H -6.712519 -0.174188 0.775824 C -3.425619 -2.086849 -0.116716 H -4.270053 -2.745674 0.053027 C -2.170297 -2.648359 -0.404051 H -2.070143 -3.730948 -0.432599 C -1.067828 -1.830904 -0.635256 C 0.357679 -2.322847 -0.826502 H 0.388547 -3.409223 -0.966065 C 1.212812 -1.912191 0.410745 H 1.003867 -2.608401 1.231826 H 0.882506 -0.924191 0.730882 C 2.712458 -1.858614 0.252973 C 3.441390 -0.735178 0.000205 H 4.520543 -0.750425 0.119927 C 2.841376 0.537139 -0.437055 O 1.800787 0.574220 -1.085501 C 3.609834 1.830193 -0.116559 H 4.206079 2.047311 -1.014073 H 4.334986 1.627147 0.678894 C 2.775211 3.120886 0.250423 H 3.126990 3.464951 1.230089 H 3.036634 3.911441 -0.460669 O 3.263331 -3.064486 0.529994 H 0.791009 -1.857439 -1.717512 C -1.256663 -0.441593 -0.581257 H -0.407578 0.198169 -0.779905 C 4.672028 -3.229242 0.406353 H 4.863651 -4.291379 0.566495 H 5.206627 -2.643535 1.164474 H 5.016379 -2.932496 -0.591357 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.31405511 Predicted Change= 2.404490D-11 Zero-point correction (ZPE)= -1113.9249 0.38911 Internal Energy (U)= -1113.9034 0.41058


S124

S124

Enthalpy (H)= -1113.9025 0.41152 Gibbs Free Energy (G)= -1113.9746 0.33941 ------------------------------------------------------------------------------ Frequencies -- -130.0059 34.4648 40.7030

5.8.12 TSc→ca Supporting Information: c-015-pAnsa-mAnsa2-pCO-E-Garugamblin-1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.30889979 Predicted Change= -3.714879D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00035 || 0.00180 [ YES ] 0.00035 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.122947 2.022667 1.506815 H -1.768074 1.654546 2.301363 C 0.252647 1.817567 1.596060 H 0.687168 1.279134 2.432731 C 1.061076 2.173079 0.517882 O 2.345369 1.648573 0.426103 C 2.351055 0.324588 0.000166 C 0.539640 2.905491 -0.546697 H 1.193914 3.198601 -1.361712 C -0.836663 3.118519 -0.614110 H -1.251912 3.605749 -1.492934 C -1.695127 2.596872 0.364097 C 3.577046 -0.371694 0.065311 O 4.647996 0.338894 0.527105 C 5.897711 -0.322526 0.598653 H 6.232857 -0.665596 -0.389874 H 5.864230 -1.182182 1.282313 H 6.605034 0.415243 0.982613 C 3.603451 -1.709934 -0.334104 H 4.533031 -2.266852 -0.293438 C 2.438493 -2.357649 -0.773469 H 2.493474 -3.406020 -1.057770 C 1.227458 -1.672804 -0.845667 C -0.084418 -2.327425 -1.244680 H -0.605248 -1.694864 -1.964000 C -1.003211 -2.616798 -0.019250 H -0.442118 -2.406870 0.902143 H -1.206563 -3.692160 0.027694 C -2.368378 -1.979194 0.218386 C -2.991391 -0.830054 -0.177275 H -3.946844 -0.628671 0.295283 C -2.607919 0.218960 -1.128323 O -1.685882 0.152385 -1.937494 C -3.465696 1.497686 -1.099155 H -4.533685 1.240799 -1.097654 H -3.248622 2.019912 -2.035002 C -3.179899 2.452711 0.103435 H -3.653085 3.417614 -0.121312 H -3.668806 2.067189 1.005780 O -2.971721 -2.802147 1.124737 H 0.127383 -3.283812 -1.735818 C 1.214355 -0.321722 -0.472576 H 0.284301 0.219579 -0.563436 C -4.249739 -2.497511 1.667971 H -4.484230 -3.325195 2.339390 H -5.012952 -2.433424 0.883266 H -4.230602 -1.559332 2.235941 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.30889979 Predicted Change= -3.714879D-10 Zero-point correction (ZPE)= -1113.9195 0.38939 Internal Energy (U)= -1113.8980 0.41081 Enthalpy (H)= -1113.8971 0.41175 Gibbs Free Energy (G)= -1113.9693 0.33957

------------------------------------------------------------------------------ Frequencies -- -72.4642 24.1007 49.9658

5.8.13 TSc→cb Supporting Information: c-015-pAnsa-CO-pCO-E-Garugamblin-1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest,nofreeze) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.31009851 Predicted Change= -1.895924D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00062 || 0.00180 [ YES ] 0.00062 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -0.370712 3.022806 1.297315 H -0.947499 3.189484 2.204781 C 0.925426 2.514232 1.403858 H 1.359899 2.286375 2.372700 C 1.602401 2.143419 0.244569 O 2.728119 1.322621 0.323346 C 2.434981 -0.039022 0.296117 C 1.092965 2.500691 -1.005829 H 1.663915 2.262323 -1.898215 C -0.188503 3.039809 -1.094594 H -0.617101 3.220989 -2.078509 C -0.986025 3.183090 0.050386 C 3.474384 -0.932363 -0.041878 O 4.696443 -0.374376 -0.287101 C 5.762367 -1.240754 -0.629160 H 5.556448 -1.792322 -1.557005 H 5.975014 -1.960143 0.173653 H 6.633458 -0.599384 -0.777536 C 3.181868 -2.298792 -0.107957 H 3.964062 -3.003743 -0.367222 C 1.886464 -2.780911 0.138719 H 1.698703 -3.849540 0.060408 C 0.858811 -1.904241 0.482340 C -0.582438 -2.328111 0.731006 H -0.623720 -3.366606 1.079325 C -1.506757 -2.179337 -0.530319 H -1.535823 -3.133311 -1.068682 H -1.074668 -1.423458 -1.184090 C -2.942554 -1.797397 -0.239168 C -3.460823 -0.530514 -0.183300 H -4.529084 -0.380855 -0.071421 C -2.604555 0.651784 -0.303060 O -1.386134 0.547920 -0.207663 C -3.207392 2.023800 -0.648869 H -4.276882 2.057692 -0.406956 H -3.148463 2.083974 -1.745709 C -2.499688 3.283005 -0.038876 H -2.811421 4.146381 -0.641833 H -2.899345 3.452012 0.968062 O -3.695041 -2.911066 -0.085967 H -0.990081 -1.709003 1.536395 C 1.172770 -0.540438 0.578800 H 0.383076 0.145589 0.832170 C -5.080631 -2.787562 0.221493 H -5.447864 -3.806808 0.349809 H -5.624412 -2.301057 -0.597228 H -5.229477 -2.218529 1.146624 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.31009851 Predicted Change= -1.895924D-09 Zero-point correction (ZPE)= -1113.9209 0.38912 Internal Energy (U)= -1113.8997 0.41032 Enthalpy (H)= -1113.8988 0.41126 Gibbs Free Energy (G)= -1113.9700 0.34006 ------------------------------------------------------------------------------ Frequencies -- -62.1835 27.6193 48.9255


S125

S125

5.8.14 Intac Supporting Information: a-020-mAnsa-pAnsa-pCO-E-Garugamblin-1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.32122655 Predicted Change= -3.113570D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00124 || 0.00180 [ YES ] 0.00124 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 1.502511 -2.074736 1.351670 H 1.916961 -1.862648 2.335158 C 0.120868 -2.166031 1.199629 H -0.552242 -2.006468 2.036703 C -0.410086 -2.335040 -0.077426 O -1.757905 -2.064279 -0.288188 C -2.001920 -0.700888 -0.442567 C 0.426978 -2.614823 -1.156941 H -0.007543 -2.791382 -2.136170 C 1.809004 -2.506029 -0.990947 H 2.454592 -2.617692 -1.858798 C 2.359510 -2.136422 0.244648 C -3.298331 -0.228349 -0.152851 O -4.205376 -1.164392 0.252299 C -5.521847 -0.728347 0.540603 H -6.002673 -0.280359 -0.339638 H -5.537530 -0.002156 1.365032 H -6.074216 -1.622053 0.837255 C -3.554203 1.139747 -0.293502 H -4.543066 1.527811 -0.075632 C -2.551185 2.026365 -0.709241 H -2.789447 3.082793 -0.808371 C -1.269740 1.563792 -1.006435 C -0.140699 2.440844 -1.510139 H 0.456960 1.867964 -2.223902 C 0.846122 3.022498 -0.451965 H 0.369527 3.863231 0.062350 H 1.715547 3.394547 -1.000933 C 1.324697 2.091675 0.636943 C 2.288208 1.128151 0.568562 H 2.526080 0.571506 1.465728 C 3.005127 0.732307 -0.643255 O 2.833297 1.262780 -1.741194 C 4.060448 -0.391685 -0.545649 H 5.003271 0.070460 -0.216676 H 4.223460 -0.709346 -1.579867 C 3.783393 -1.629527 0.356777 H 4.511320 -2.403427 0.078300 H 3.990306 -1.384032 1.405337 O 0.656172 2.376275 1.778751 H -0.550991 3.299882 -2.054995 C -1.024593 0.191109 -0.870142 H -0.037410 -0.177597 -1.111812 C 0.894873 1.610525 2.955391 H 0.212890 2.008579 3.708289 H 1.929932 1.725433 3.299951 H 0.679961 0.551059 2.780384 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.32122655 Predicted Change= -3.113570D-09 Zero-point correction (ZPE)= -1113.9313 0.38989 Internal Energy (U)= -1113.9093 0.41191 Enthalpy (H)= -1113.9083 0.41285 Gibbs Free Energy (G)= -1113.9816 0.33955 ------------------------------------------------------------------------------ Frequencies -- 27.8678 43.5353 62.5754

5.8.15 Intba Supporting Information: b-020-CO-mAnsa2-pCO-E-Garugamblin-1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.32663654 Predicted Change= -4.304539D-09 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00231 || 0.00180 [ NO ] 0.00231 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.708350 -2.517899 -0.836310 H -2.326160 -2.711985 -1.709169 C -0.320443 -2.518751 -0.977167 H 0.146918 -2.704815 -1.939111 C 0.474671 -2.166889 0.111649 O 1.829076 -1.926212 -0.072741 C 2.158656 -0.585408 -0.207844 C -0.093850 -1.959612 1.367123 H 0.548604 -1.721429 2.209298 C -1.481174 -1.958683 1.490988 H -1.929432 -1.728186 2.455240 C -2.309566 -2.164239 0.379953 C 3.519016 -0.251092 -0.064361 O 4.371564 -1.286148 0.192846 C 5.747816 -0.986713 0.340523 H 5.927990 -0.308587 1.186186 H 6.166512 -0.539598 -0.571497 H 6.241995 -1.940958 0.533124 C 3.888012 1.091691 -0.184779 H 4.927450 1.379701 -0.073176 C 2.930380 2.078417 -0.438236 H 3.252347 3.114398 -0.518463 C 1.580008 1.754701 -0.592175 C 0.565109 2.851463 -0.887559 H 0.632575 3.618226 -0.107270 C -0.909738 2.437429 -1.064257 H -1.032655 1.662645 -1.822361 H -1.451943 3.307429 -1.462701 C -1.645948 2.006718 0.185051 C -2.674492 1.112918 0.248437 H -3.115315 0.892296 1.214184 C -3.218347 0.353745 -0.884134 O -2.928257 0.562555 -2.060894 C -4.231660 -0.761957 -0.567956 H -4.453385 -1.225580 -1.533114 H -5.165459 -0.300977 -0.214716 C -3.788155 -1.841813 0.463162 H -4.015299 -1.504167 1.481096 H -4.406515 -2.734073 0.296253 O -1.172613 2.663965 1.267364 H 0.860981 3.350802 -1.820367 C 1.217171 0.407733 -0.479317 H 0.181617 0.120172 -0.598324 C -1.733058 2.413716 2.551596 H -1.178193 3.047729 3.244710 H -1.610442 1.361607 2.833233 H -2.796705 2.679217 2.578026 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.32663654 Predicted Change= -4.304539D-09 Zero-point correction (ZPE)= -1113.9373 0.38925 Internal Energy (U)= -1113.9151 0.41151 Enthalpy (H)= -1113.9141 0.41245 Gibbs Free Energy (G)= -1113.9888 0.33778 ------------------------------------------------------------------------------ Frequencies -- 18.9424 31.8771 60.3754


S126

S126

5.8.16 Intbc Supporting Information: b-020-CO-pAnsa-pCO-E-Garugamblin-1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.31837507 Predicted Change= -2.181077D-08 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00104 || 0.00180 [ YES ] 0.00104 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.339251 3.244599 -0.968759 H 0.777891 3.644500 -1.879520 C -0.986432 2.811804 -0.990782 H -1.578833 2.864775 -1.899061 C -1.505020 2.164957 0.127530 O -2.687753 1.436417 0.015980 C -2.471978 0.078055 -0.178798 C -0.775119 2.120206 1.316101 H -1.214017 1.653083 2.192635 C 0.546872 2.565338 1.323591 H 1.133773 2.456401 2.233429 C 1.152352 3.042408 0.152348 C -3.563852 -0.796031 0.020671 O -4.752285 -0.208048 0.345912 C -5.869919 -1.050575 0.560071 H -5.702262 -1.742703 1.396885 H -6.119015 -1.630935 -0.338972 H -6.702382 -0.387100 0.802531 C -3.350030 -2.170026 -0.114068 H -4.171807 -2.860425 0.040272 C -2.076673 -2.682161 -0.413321 H -1.940339 -3.759649 -0.468967 C -1.002095 -1.823754 -0.624684 C 0.434720 -2.269926 -0.842312 H 0.492314 -3.350446 -1.014732 C 1.291053 -1.872460 0.395144 H 1.077614 -2.572397 1.212183 H 0.960841 -0.887270 0.726346 C 2.792609 -1.824555 0.241297 C 3.521411 -0.694691 0.043041 H 4.599693 -0.702907 0.174196 C 2.898836 0.595382 -0.329777 O 1.986253 0.652778 -1.145184 C 3.417153 1.857504 0.371970 H 4.487289 1.975911 0.144935 H 3.378030 1.659491 1.452278 C 2.662234 3.168115 0.037344 H 3.051680 3.950582 0.703338 H 2.912156 3.475300 -0.983884 O 3.334962 -3.046933 0.468587 H 0.847816 -1.766868 -1.722823 C -1.235787 -0.442313 -0.536611 H -0.408510 0.229551 -0.722119 C 4.742059 -3.208591 0.335358 H 4.933284 -4.277349 0.444469 H 5.279589 -2.660429 1.119584 H 5.085917 -2.864540 -0.647486 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.31837507 Predicted Change= -2.181077D-08 Zero-point correction (ZPE)= -1113.9293 0.38901 Internal Energy (U)= -1113.9071 0.41120 Enthalpy (H)= -1113.9062 0.41214 Gibbs Free Energy (G)= -1113.9800 0.33837 ------------------------------------------------------------------------------ Frequencies -- 32.5444 42.7595 62.6510

5.8.17 Intca Supporting Information: c-020-pAnsa-mAnsa2-pCO-E-Garugamblin-1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.31745780 Predicted Change= -1.653297D-08 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00002 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00096 || 0.00180 [ YES ] 0.00096 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -0.617392 2.180875 1.524107 H -1.143271 1.872691 2.425462 C 0.729427 1.855274 1.378952 H 1.251765 1.285735 2.141511 C 1.375639 2.143783 0.175762 O 2.594689 1.534160 -0.115240 C 2.471598 0.157471 -0.283632 C 0.743639 2.927974 -0.786970 H 1.271352 3.174829 -1.702988 C -0.601401 3.263019 -0.617909 H -1.114359 3.790768 -1.418561 C -1.326511 2.812266 0.493064 C 3.596547 -0.657910 -0.037221 O 4.755684 -0.010841 0.281266 C 5.903080 -0.799190 0.540281 H 6.185298 -1.404070 -0.332362 H 5.753294 -1.463949 1.402308 H 6.705905 -0.094092 0.764569 C 3.437888 -2.045404 -0.116004 H 4.283775 -2.695497 0.078452 C 2.186549 -2.620648 -0.392085 H 2.091319 -3.704084 -0.385045 C 1.080412 -1.816617 -0.655430 C -0.345014 -2.321437 -0.823692 H -0.779830 -1.902538 -1.735810 C -1.199371 -1.851536 0.395408 H -0.859310 -0.853526 0.671929 H -0.994962 -2.513139 1.245417 C -2.701268 -1.782593 0.249816 C -3.415754 -0.675626 -0.108887 H -4.493005 -0.658932 0.021507 C -2.798442 0.519763 -0.697041 O -1.737607 0.466607 -1.317320 C -3.491167 1.880996 -0.558776 H -4.556960 1.770357 -0.324912 H -3.410657 2.365380 -1.537835 C -2.842433 2.821160 0.515971 H -3.243631 3.828573 0.344700 H -3.185688 2.512922 1.510361 O -3.271665 -2.938660 0.660330 H -0.370887 -3.413798 -0.906816 C 1.266937 -0.426301 -0.647031 H 0.419119 0.206101 -0.872905 C -4.686928 -3.082650 0.586869 H -4.895634 -4.117471 0.862405 H -5.049786 -2.884256 -0.428334 H -5.188859 -2.408154 1.291345 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.31745780 Predicted Change= -1.653297D-08 Zero-point correction (ZPE)= -1113.9277 0.38972 Internal Energy (U)= -1113.9057 0.41173 Enthalpy (H)= -1113.9047 0.41267 Gibbs Free Energy (G)= -1113.9780 0.33945 ------------------------------------------------------------------------------ Frequencies -- 36.1671 41.2442 61.2708


S127

S127

5.8.18 Intcb Supporting Information: c-020-pAnsa-CO-pCO-E-Garugamblin-1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.31837498 Predicted Change= -8.520906D-09 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00001 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00119 || 0.00180 [ YES ] 0.00119 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.338839 3.244305 -0.969102 H 0.777098 3.644025 -1.880124 C -0.986869 2.811560 -0.990470 H -1.579644 2.864368 -1.898514 C -1.505005 2.164926 0.128173 O -2.687769 1.436372 0.017208 C -2.472014 0.078070 -0.177952 C -0.774583 2.120303 1.316432 H -1.213110 1.653309 2.193221 C 0.547401 2.565489 1.323303 H 1.134697 2.456702 2.232904 C 1.152376 3.042412 0.151733 C -3.563905 -0.796050 0.021266 O -4.752341 -0.208129 0.346611 C -5.869982 -1.050696 0.560564 H -5.702351 -1.743009 1.397229 H -6.119065 -1.630856 -0.338611 H -6.702447 -0.387269 0.803154 C -3.350088 -2.170012 -0.113789 H -4.171878 -2.860439 0.040352 C -2.076731 -2.682091 -0.413146 H -1.940413 -3.759566 -0.469068 C -1.002126 -1.823649 -0.624213 C 0.434670 -2.269788 -0.842049 H 0.492232 -3.350309 -1.014471 C 1.291248 -1.872347 0.395260 H 1.078031 -2.572297 1.212333 H 0.961127 -0.887149 0.726556 C 2.792764 -1.824436 0.241053 C 3.521483 -0.694621 0.042332 H 4.599816 -0.702799 0.173035 C 2.898660 0.595337 -0.330503 O 1.985811 0.652506 -1.145632 C 3.417117 1.857589 0.370856 H 4.487213 1.975933 0.143614 H 3.378189 1.659799 1.451232 C 2.662197 3.168115 0.036094 H 3.051870 3.950659 0.701857 H 2.911806 3.475139 -0.985268 O 3.335181 -3.046836 0.468234 H 0.847608 -1.766741 -1.722640 C -1.235795 -0.442228 -0.535765 H -0.408496 0.229668 -0.721056 C 4.742236 -3.208555 0.334686 H 4.933448 -4.277305 0.443898 H 5.279982 -2.660312 1.118705 H 5.085870 -2.864652 -0.648291 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.31837498 Predicted Change= -8.520906D-09 Zero-point correction (ZPE)= -1113.9293 0.38901 Internal Energy (U)= -1113.9071 0.41120 Enthalpy (H)= -1113.9062 0.41214 Gibbs Free Energy (G)= -1113.9800 0.33837 ------------------------------------------------------------------------------ Frequencies -- 32.5128 42.7750 62.6694

5.8.19 TSac→acb Supporting Information: a-020-mAnsa-pAnsa-CO-pCO-E-Garugamblin-1-TS2.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.31139957 Predicted Change= -1.685572D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00027 || 0.00180 [ YES ] 0.00027 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -0.139566 2.716216 1.362855 H -0.566333 2.670895 2.362682 C 1.133755 2.196385 1.147296 H 1.702128 1.752535 1.959076 C 1.626973 2.117857 -0.155022 O 2.737928 1.315657 -0.423217 C 2.447904 -0.047082 -0.385927 C 0.949599 2.753830 -1.195764 H 1.375516 2.741597 -2.194755 C -0.325291 3.275863 -0.962340 H -0.892825 3.672118 -1.802503 C -0.934033 3.151513 0.293672 C 3.468768 -0.946499 -0.014944 O 4.694484 -0.402959 0.242607 C 5.740636 -1.279197 0.619675 H 5.956457 -2.016087 -0.166151 H 5.509535 -1.810573 1.553350 H 6.618684 -0.648461 0.772397 C 3.152257 -2.307300 0.073684 H 3.917644 -3.020183 0.360004 C 1.850332 -2.770118 -0.172187 H 1.640525 -3.831850 -0.061770 C 0.840437 -1.885652 -0.551209 C -0.611117 -2.291188 -0.768793 H -1.025687 -1.683061 -1.578184 C -1.500214 -2.098083 0.511457 H -1.064629 -1.298834 1.109571 H -1.488764 -3.021870 1.100290 C -2.954268 -1.759202 0.254327 C -3.485169 -0.510568 0.062372 H -4.557889 -0.379578 -0.027792 C -2.633791 0.674855 -0.048943 O -1.413464 0.560803 -0.101536 C -3.245542 2.077894 -0.196097 H -4.281081 2.100068 0.165461 H -3.297688 2.259431 -1.279736 C -2.440319 3.248529 0.466872 H -2.834729 4.183580 0.047769 H -2.674106 3.266204 1.538109 O -3.705341 -2.883376 0.286627 H -0.676573 -3.337497 -1.089668 C 1.183759 -0.532793 -0.687284 H 0.417401 0.168763 -0.972538 C -5.107353 -2.800607 0.046922 H -5.474378 -3.827461 0.078086 H -5.312775 -2.361146 -0.936212 H -5.605822 -2.207504 0.822930 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.31139957 Predicted Change= -1.685572D-10 Zero-point correction (ZPE)= -1113.9221 0.38921 Internal Energy (U)= -1113.9010 0.41033 Enthalpy (H)= -1113.9001 0.41127 Gibbs Free Energy (G)= -1113.9709 0.34041 ------------------------------------------------------------------------------ Frequencies -- -60.1309 32.1927 46.5196


S128

S128

5.8.20 TSba→bac Supporting Information: b-020-CO-mAnsa2-pAnsa-pCO-E-Garugamblin-1-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.32536551 Predicted Change= -2.432719D-11 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00015 || 0.00180 [ YES ] 0.00015 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.771112 -2.544800 -0.889468 H -2.381680 -2.753073 -1.763923 C -0.381986 -2.543218 -1.012442 H 0.099653 -2.746895 -1.963702 C 0.397330 -2.179225 0.083618 O 1.760586 -1.970903 -0.078324 C 2.123623 -0.642225 -0.234488 C -0.189053 -1.944272 1.326185 H 0.442720 -1.697662 2.174027 C -1.577759 -1.952820 1.434183 H -2.040160 -1.722110 2.391689 C -2.389458 -2.188994 0.316679 C 3.480287 -0.326297 -0.026212 O 4.298516 -1.367285 0.307384 C 5.670505 -1.087020 0.518024 H 5.819498 -0.387130 1.352015 H 6.143933 -0.674481 -0.383469 H 6.136372 -2.043329 0.763715 C 3.879384 1.006294 -0.161705 H 4.915486 1.280678 0.002525 C 2.954031 2.001025 -0.492916 H 3.296619 3.029752 -0.580034 C 1.609670 1.693653 -0.715363 C 0.633014 2.790953 -1.113733 H 0.768885 3.646624 -0.442880 C -0.863783 2.426114 -1.174570 H -1.064608 1.608394 -1.867811 H -1.395867 3.293937 -1.592044 C -1.528557 2.105161 0.144172 C -2.563485 1.237853 0.338843 H -2.971512 1.134724 1.337908 C -3.192842 0.389962 -0.682297 O -2.884171 0.380067 -1.873134 C -4.325704 -0.533362 -0.202559 H -4.959574 -0.696796 -1.077705 H -4.928721 -0.011051 0.549691 C -3.878515 -1.932450 0.381214 H -4.210020 -2.004126 1.422586 H -4.416285 -2.713099 -0.167726 O -0.994766 2.849663 1.137725 H 0.904024 3.152582 -2.115742 C 1.216548 0.356561 -0.586763 H 0.184477 0.081061 -0.756181 C -1.474821 2.706824 2.470380 H -0.871791 3.385158 3.075682 H -1.344397 1.678093 2.825139 H -2.532276 2.988120 2.542345 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.32536551 Predicted Change= -2.432719D-11 Zero-point correction (ZPE)= -1113.9359 0.38939 Internal Energy (U)= -1113.9144 0.41088 Enthalpy (H)= -1113.9135 0.41182 Gibbs Free Energy (G)= -1113.9862 0.33910 ------------------------------------------------------------------------------ Frequencies -- -75.1423 20.9363 31.5381

5.8.21 TSbc→bca Supporting Information: b-020-CO-pAnsa-mAnsa-pCO-E-Garugamblin-1-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.30847890 Predicted Change= -1.253736D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00013 || 0.00180 [ YES ] 0.00013 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.316938 3.206226 -0.942563 H 0.626743 3.556234 -1.923685 C -1.008250 2.823014 -0.745079 H -1.728246 2.856405 -1.556921 C -1.363424 2.219277 0.458840 O -2.536666 1.474285 0.530711 C -2.368905 0.173191 0.072015 C -0.471389 2.193661 1.529006 H -0.783536 1.755928 2.472376 C 0.846608 2.600218 1.321349 H 1.562764 2.497477 2.133922 C 1.281547 3.010515 0.052899 C -3.494930 -0.676218 0.123639 O -4.638430 -0.127566 0.630230 C -5.793000 -0.944815 0.689576 H -5.637379 -1.822272 1.332457 H -6.102435 -1.283966 -0.308647 H -6.579695 -0.320282 1.117462 C -3.363607 -1.986609 -0.342333 H -4.217102 -2.655085 -0.319875 C -2.142975 -2.455811 -0.849117 H -2.081785 -3.479647 -1.211336 C -1.025851 -1.623348 -0.899286 C 0.329290 -2.079726 -1.414602 H 0.176543 -2.860046 -2.169073 C 1.243620 -2.673834 -0.305095 H 1.500282 -3.707342 -0.562574 H 0.665798 -2.761844 0.625520 C 2.569365 -2.061428 0.126312 C 3.133850 -0.822093 0.060108 H 4.045763 -0.701432 0.636391 C 2.742027 0.435957 -0.596660 O 1.981805 0.550167 -1.552106 C 3.438891 1.677739 0.001384 H 4.470484 1.695175 -0.383169 H 3.532895 1.534649 1.084893 C 2.756951 3.032422 -0.296936 H 3.299155 3.808617 0.260464 H 2.867680 3.268865 -1.359853 O 3.192879 -3.059435 0.820511 H 0.831376 -1.247371 -1.909734 C -1.163960 -0.309637 -0.431892 H -0.304452 0.341270 -0.494006 C 4.456613 -2.855225 1.437206 H 4.728371 -3.819830 1.869298 H 4.398471 -2.102841 2.233608 H 5.215145 -2.553119 0.705092 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.30847890 Predicted Change= -1.253736D-10 Zero-point correction (ZPE)= -1113.9192 0.38927 Internal Energy (U)= -1113.8978 0.41067 Enthalpy (H)= -1113.8968 0.41161 Gibbs Free Energy (G)= -1113.9687 0.33969 ------------------------------------------------------------------------------ Frequencies -- -72.2335 25.0914 48.1322


S129

S129

5.8.22 TSca→cab Supporting Information: c-020-pAnsa-mAnsa2-CO-pCO-E-Garugamblin-1-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.31139958 Predicted Change= -2.449029D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00030 || 0.00180 [ YES ] 0.00030 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -0.139593 2.716208 1.362859 H -0.566366 2.670887 2.362682 C 1.133730 2.196380 1.147309 H 1.702099 1.752529 1.959091 C 1.626959 2.117859 -0.155007 O 2.737922 1.315666 -0.423198 C 2.447907 -0.047072 -0.385914 C 0.949593 2.753835 -1.195751 H 1.375518 2.741608 -2.194739 C -0.325300 3.275864 -0.962336 H -0.892828 3.672121 -1.802503 C -0.934053 3.151510 0.293671 C 3.468777 -0.946485 -0.014943 O 4.694490 -0.402939 0.242612 C 5.740648 -1.279172 0.619676 H 5.956476 -2.016054 -0.166156 H 5.509547 -1.810558 1.553346 H 6.618690 -0.648431 0.772405 C 3.152277 -2.307289 0.073671 H 3.917669 -3.020170 0.359982 C 1.850355 -2.770115 -0.172203 H 1.640556 -3.831849 -0.061796 C 0.840453 -1.885651 -0.551212 C -0.611101 -2.291191 -0.768798 H -1.025672 -1.683068 -1.578191 C -1.500198 -2.098083 0.511452 H -1.064616 -1.298831 1.109561 H -1.488743 -3.021866 1.100289 C -2.954257 -1.759211 0.254330 C -3.485172 -0.510581 0.062379 H -4.557892 -0.379602 -0.027765 C -2.633805 0.674847 -0.048965 O -1.413479 0.560801 -0.101599 C -3.245564 2.077885 -0.196103 H -4.281099 2.100052 0.165468 H -3.297722 2.259427 -1.279740 C -2.440340 3.248522 0.466864 H -2.834750 4.183572 0.047759 H -2.674129 3.266199 1.538100 O -3.705322 -2.883390 0.286642 H -0.676553 -3.337503 -1.089670 C 1.183766 -0.532788 -0.687276 H 0.417404 0.168764 -0.972522 C -5.107339 -2.800631 0.046943 H -5.474355 -3.827488 0.078106 H -5.312768 -2.361168 -0.936190 H -5.605807 -2.207533 0.822954 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.31139958 Predicted Change= -2.449029D-10 Zero-point correction (ZPE)= -1113.9221 0.38921 Internal Energy (U)= -1113.9010 0.41033 Enthalpy (H)= -1113.9001 0.41127 Gibbs Free Energy (G)= -1113.9709 0.34041 ------------------------------------------------------------------------------ Frequencies -- -60.1335 32.1923 46.5208

5.8.23 TScb→cba Supporting Information: c-020-pAnsa-CO-mAnsa-pCO-E-Garugamblin-1-TS.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250,calcfc,ts,noeigentest) freq=noraman #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.30847890 Predicted Change= -1.247457D-10 ============================================================================== Optimization completed. {Found 2 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00000 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00012 || 0.00180 [ YES ] 0.00012 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C 0.316939 3.206224 -0.942564 H 0.626742 3.556230 -1.923687 C -1.008249 2.823012 -0.745077 H -1.728246 2.856402 -1.556918 C -1.363421 2.219276 0.458844 O -2.536663 1.474284 0.530717 C -2.368904 0.173191 0.072019 C -0.471384 2.193661 1.529008 H -0.783530 1.755930 2.472379 C 0.846612 2.600219 1.321348 H 1.562770 2.497478 2.133920 C 1.281550 3.010514 0.052897 C -3.494931 -0.676216 0.123640 O -4.638430 -0.127562 0.630231 C -5.793002 -0.944809 0.689572 H -5.637384 -1.822269 1.332450 H -6.102436 -1.283956 -0.308653 H -6.579697 -0.320275 1.117458 C -3.363610 -1.986606 -0.342335 H -4.217107 -2.655080 -0.319881 C -2.142978 -2.455809 -0.849120 H -2.081790 -3.479644 -1.211342 C -1.025852 -1.623348 -0.899285 C 0.329288 -2.079727 -1.414602 H 0.176541 -2.860047 -2.169072 C 1.243619 -2.673834 -0.305095 H 1.500280 -3.707343 -0.562574 H 0.665797 -2.761844 0.625521 C 2.569363 -2.061429 0.126312 C 3.133850 -0.822094 0.060107 H 4.045762 -0.701433 0.636390 C 2.742028 0.435955 -0.596662 O 1.981804 0.550165 -1.552109 C 3.438893 1.677737 0.001379 H 4.470486 1.695173 -0.383176 H 3.532899 1.534649 1.084888 C 2.756952 3.032420 -0.296941 H 3.299158 3.808616 0.260458 H 2.867680 3.268862 -1.359858 O 3.192876 -3.059436 0.820513 H 0.831374 -1.247371 -1.909734 C -1.163959 -0.309639 -0.431888 H -0.304450 0.341267 -0.493999 C 4.456609 -2.855226 1.437210 H 4.728367 -3.819831 1.869303 H 4.398466 -2.102841 2.233612 H 5.215143 -2.553120 0.705097 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.30847890 Predicted Change= -1.247457D-10 Zero-point correction (ZPE)= -1113.9192 0.38927 Internal Energy (U)= -1113.8978 0.41067 Enthalpy (H)= -1113.8968 0.41161 Gibbs Free Energy (G)= -1113.9687 0.33969 ------------------------------------------------------------------------------ Frequencies -- -72.2336 25.0913 48.1322


S130

S130

5.8.24 ent- C11-E-Garugamblin I Supporting Information: a-020-mAnsa-CO2-pCO-E-Garugamblin-1.log ------------------------------------------------------------------------------ Using Gaussian 09: AM64L-G09RevC.01 23-Sep-2011 ============================================================================== # b3lyp/6-31G* gfprint gfinput scf=(direct,tight,maxcycle=300,xqc) opt=(maxcycle=250) freq=noraman geom=connectivity #N Geom=AllCheck Guess=TCheck SCRF=Check GenChk RB3LYP/6-31G(d) Freq ------------------------------------------------------------------------------ Pointgroup= C1 Stoichiometry= C21H22O4 C1[X(C21H22O4)] #Atoms= 47 Charge = 0 Multiplicity = 1 ------------------------------------------------------------------------------ SCF Energy= -1114.33019521 Predicted Change= -1.503282D-07 ============================================================================== Optimization completed. {Found 1 times} Item Max Val. Criteria Pass? RMS Val. Criteria Pass? Force 0.00004 || 0.00045 [ YES ] 0.00000 || 0.00030 [ YES ] Displ 0.00299 || 0.00180 [ NO ] 0.00299 || 0.00180 [ YES ] ------------------------------------------------------------------------------ Atomic Coordinates (Angstroms) Type X Y Z ------------------------------------------------------------------------------ C -1.672188 -2.568204 -1.070872 H -2.205235 -2.690681 -2.009648 C -0.277613 -2.553455 -1.073680 H 0.283943 -2.665573 -1.996077 C 0.399314 -2.267087 0.109221 O 1.762880 -2.003768 0.082629 C 2.096562 -0.682306 -0.168576 C -0.293138 -2.154247 1.314006 H 0.261137 -1.970175 2.229279 C -1.686070 -2.195936 1.304732 H -2.226620 -2.051358 2.237842 C -2.396780 -2.326510 0.102586 C 3.446676 -0.329413 0.031806 O 4.274256 -1.330462 0.452957 C 5.640218 -1.016611 0.654556 H 5.771520 -0.253459 1.434213 H 6.117651 -0.667430 -0.271269 H 6.115641 -1.945114 0.976722 C 3.829669 0.993556 -0.200424

H 4.859568 1.294836 -0.044121 C 2.897458 1.945527 -0.627098 H 3.229790 2.966906 -0.798603 C 1.561689 1.602368 -0.842676 C 0.586191 2.639061 -1.383136 H 0.783011 3.598477 -0.892807 C -0.921104 2.322441 -1.295398 H -1.189871 1.415993 -1.840250 H -1.459061 3.131495 -1.811025 C -1.492287 2.230126 0.098609 C -2.509527 1.417818 0.506024 H -2.801223 1.442700 1.549493 C -3.234203 0.446990 -0.322918 O -3.149747 0.364196 -1.547468 C -4.148765 -0.535301 0.431689 H -5.190378 -0.285249 0.187725 H -4.035012 -0.411366 1.514218 C -3.877267 -2.011826 0.036639 H -4.464028 -2.661154 0.699517 H -4.237392 -2.176630 -0.982942 O -0.865237 3.094887 0.925571 H 0.804189 2.798802 -2.448998 C 1.180392 0.276024 -0.600946 H 0.151655 -0.020423 -0.751440 C -1.252409 3.182720 2.292768 H -0.605714 3.942527 2.733894 H -1.100466 2.225921 2.805438 H -2.301234 3.487716 2.387849 ------------------------------------------------------------------------------ Statistical Thermodynamic Analysis Temperature= 298.150 Kelvin Pressure= 1.00000 Atm ============================================================================== SCF Energy= -1114.33019521 Predicted Change= -1.503282D-07 Zero-point correction (ZPE)= -1113.9406 0.38955 Internal Energy (U)= -1113.9184 0.41170 Enthalpy (H)= -1113.9175 0.41264 Gibbs Free Energy (G)= -1113.9920 0.33811 ------------------------------------------------------------------------------ Frequencies -- 15.5520 31.3967 51.7666

the nature of persistent conformational chirality ... · supporting*information* s1* supporting...

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the nature of persistent conformational chirality ... · supportinginformation s1* supporting...