total synthesis of (±)-pallambins c and d · supplementary information for total synthesis of...

Supplementary Information for

Total Synthesis of (±)-Pallambins C and D

Xue-Song Xu, Zhen-Wu Li, Yi-Jun Zhang, Xiao-Shui Peng, and Henry N. C. Wong*

Table of contents General information……………………………………………………………………………….S2

Synthesis of compound 6………………………………………………………………………….S3

Synthesis of compound 6a………………………………………………………….......................S4




Synthesis of compound 9a………………………………………………………….......................S6

Synthesis of compound 9b………………………………………………………….......................S6

Synthesis of compound 10………………………………………………………….......................S7

Synthesis of compound 10a……………………………………………………….........................S7



Synthesis of compound 12a……………………………………………………………………….S9

Synthesis of compound 13……………………………………………………………………….S10

Synthesis of compound 13a……………………………………………………….......................S10




Synthesis of compound 15b……………………………………………………….......................S13



Synthesis of compound 4………………………………………………………...........................S14

Synthesis of compound 17……………………………………………………….........................S15













Synthesis of pallambin C (1)…………………………………………………………………….S22


Synthesis of pallambin D (2)……………………………………………………….....................S23

NMR spectra and basic crystal data…………..…………………….....................................S24-S70

1

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2012

General Information

Unless stated otherwise, all reactions were carried out under an argon atmosphere under anhydrous conditions and all reagents were purchased from commercial suppliers without further purification. Solvent drying by standard methods were employed when necessary. The plates used for thin-layer chromatography (TLC) were E. Merck silica gel 60F254 (0.24 nm thickness) precoated on aluminum plates, and then visualized under UV light (365 nm and 254 nm) or through staining with a 5% of dodecamolybdophosphoric acid in ethanol and subsequent heating. Column chromatography was performed using E. Merck silica gel (230-400 mesh). Melting points were measured on an Electrothermal 9100 apparatus without correction. NMR spectra were recorded on a Bruker Advance III 400 spectrometer (400.00 MHz for 1H and 100 MHz for 13C) and a Bruker 400 MHz NMR AV400Q (400.00 MHz for 1H and 100 MHz for 13C) at room temperature. Solvent signal was used as reference for 1H, 13C NMR (CDCl3, 7.26, 77.16 ppm; C6D6, 7.16, 128.06 ppm). The following abbreviations were used to explain the multiplicities: s = singlet, d = doublet, t = triplet, q = quartet, brs = broad singlet, dd = double doublet, td = triple doublet, dt = double triplet, dq = double quartet, m = multiplet. Mass spectra (ESI, EI and FAB) were obtained with a ThermoFinnigan MAT 95 XL spectrometer and determined at an ionized voltage of 70 eV unless otherwise mentioned. Elemental analyses were performed at Shanghai Institute of Organic Chemistry, The Chinese Academy of Sciences, China. Infrared spectra (IR) were recorded on a Perkin Elmer (Spectrum One) FT-IR spectrometer.

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Experimental details and characteristic data for compounds

From Wieland-Miescher ketone to 11

OAcH

O

11

EtO

EtO

i, j

OH

HOHOAc

OH

HO

OBn

BnOO

OBn

BnOOH

OBn

BnO

6 7

89

O

O

Wieland-Miescher ketone

a b,c

10

f,g, h

d

e

X-ray structures of 10 (left) and 11 (right)

Synthesis of compound 6

To a stirred solution of (±)-Wieland-Miescher ketone (12.0 g, 67.4 mmol) and CeCl3•7H2O (37.6 g, 101 mmol) in MeOH (250 mL) at -78 °C was added NaBH4 (5.1 g, 13.5 mmol) in one portion. The reaction was stirred for 20 min at -78 °C and warmed up to rt, filtered through Celite. The filtered cake was washed with MeOH (200 mL x 2). After evaporation, the residue was partitioned between EA (500 mL) and saturated NH4Cl (500 mL), and the aqueous phase was extracted with EA (300 mL x 3). The combined organic phase was dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silical gel, Hex/EA = 2:1) to afford 6 (10.6 g, 86%) as a white solid. mp 151.0-152.0 oC. 1H NMR (400 MHz, CDCl3) δ = 5.41 (s, 1H), 4.18 (brs, 1H), 3.29-3.24 (m, 1H), 2.18-2.10 (m, 1H), 2.01-1.93 (m, 2H), 1.86-1.75 (m, 3H), 1.61-1.54 (m, 1H), 1.48-1.43 (m, 4H), 1.34-1.23 (m, 1H), 1.07 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ = 144.92, 126.06, 79.22, 67.79, 40.76, 33.64, 31.46, 30.85, 29.00, 24.71, 16.92 ppm; IR (neat) 2934, 2860, 1658, 1445, 1050, 931 cm-1; HRMS (EI) m/z Calcd for C11H18O2 [M]+: 182.1301, found 182.1306.

Synthesis of compound 6a

To a stirred solution of compound 6 (14.2 g, 78 mmol) in DMF (160 mL) at was

3


added NaH (~60%, 12.5 g, 312 mmol) in portions 0 °C. The formed mixture was stirred for 30 min at the same temperature, and then BnBr (28 mL, 234 mmol) was added dropwise during 15 min. The reaction was allowed to warm to rt and stirred for 20 h. The reaction mixture was pre-cooled in ice bath and quenched with water (500 mL), extracted with EA (300 mL x 2), washed with brine (300 mL), dried over Na2SO4, concentrated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 100:1-50:1) to afford 6a (26.8 g, 95%) as a colorless oil. 1H NMR (400 MHz, CDCl3) δ = 7.38-7.27 (m, 10H), 5.49 (s, 1H), 4.66 (d, J = 11.9 Hz, 1H), 4.62 (d, J = 11.9 Hz, 1H), 4.56 (d, J = 12.0 Hz, 1H), 4.43 (d, J = 11.9 Hz, 1H), 3.97-3.94 (m, 1H), 2.98 (dd, J = 4.2, 11.6 Hz, 1H), 2.21-2.15 (m, 1H), 2.04-1.96 (m, 4H), 1.82-1.79 (m, 1H), 1.60-1.54 (m, 2H), 1.38-1.31 (m, 1H), 1.26-1.17 (m, 1H), 1.15 (s, 3H); 13C NMR δ = (100 MHz, CDCl3) δ = 145.59, 139.40, 139.14, 128.45, 128.35, 127.81, 127.56, 127.54, 127.45, 123.39, 86.46, 74.48, 71.44, 70.05, 41.13, 34.07, 31.78, 26.74, 25.35, 24.63, 17.99 ppm;. IR (neat) 2937, 2860, 1658, 1453, 1358, 1094, 1070, 734, 696 cm-1; HRMS (EI) m/z Calcd for C25H30O2 [M]+: 362.2240, found 362.2254.


To a well stirred suspension of compound 6a (19.7 g, 54.4 mmol) and NaHCO3 (20 g, 238.1 mmol) in DCM (500 mL) was added mCPBA (~70%, 20 g, 81.4 mmol). The reaction was stirred for 3 h at rt, and then was partitioned with water (500 mL). The aqueous phase was extracted with DCM (300 mL), and the combined organic phase was washed with saturated NaHCO3 (300 mL) and brine (300 mL), dried over Na2SO4, evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 40:1-20:1) to afford 7 (17.7 g, 86%) as a colorless oil. 1H NMR (400 MHz, CDCl3) δ = 7.38-7.27 (m, 10H), 4.65 (d, J = 11.1 Hz, 1 H), 4.63 (s, 2 H), 4.44 (d, J = 11.8 Hz, 1 H), 3.72 (dd, J = 7.8, 8.1 Hz, 1 H), 3.37-3.33 (m, 1H), 3.04 (s, 1H), 2.04-1.98 (m, 2H), 1.94-1.89 (m, 1H), 1.76-1.73 (m, 1H), 1.65-1.56 (m, 3H), 1.53-1.43 (m, 1H),1.32-1.24 (m, 1H), 1.19 (s, 3H), 0.96 (d, J = 14.4 Hz, 1H) ppm; 13C NMR (100 MHz, CDCl3) δ = 139.31,138.33, 128.58, 128.35, 127.86, 127.53, 127.46, 83.69, 72.70, 71.68, 71.32, 66.62, 61.53, 38.88, 29.14, 27.56, 26.48, 24.07, 20.74, 16.25 ppm; IR (neat) 2948, 2868, 1605, 1497, 1454, 1360, 1093, 1073, 738, 702 cm-1; HRMS (ESI) m/z Calcd for C25H30O3Na [M+Na]+: 401.2087, found 401.2100; Anal. Calcd for C25H30O3: C, 79.33; H, 7.99; found C, 79.28; H, 8.15.


OBn

BnOO

OBn

BnOOH

8

CH3MgI

benzene, reflux, 12 h

7

4


To a stirred solution of MeMgI in minimized amount of Et2O [prepared from Mg turnings (5.5 g, 230 mmol) and MeI (13.7 mL, 220 mmol), and distilled off most of the solvent Et2O] was added a solution of the epoxide above (16.8 g, 44.4 mmol) in benzene (300 mL), and the reaction was stirred under reflux for 12 h. After being cooled to 0 °C, the reaction was quenched with 5% HCl (500 mL), extracted with EA (300 mL x 2). The combined organic phase was washed with saturated NaHCO3 (300 mL) and brine (300 mL), dried over Na2SO4, evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 20:1-10:1) to afford 8 (15.6 g, 89%) as a colorless oil. 1HNMR (400 MHz, CDCl3) δ = 7.37-7.27 (m, 10H), 4.61 (d, J = 11.8 Hz, 1H), 4.55 (d, J = 11.9 Hz, 1H), 4.49 (d, J = 11.9 Hz, 1H), 4.44 (d, J = 11.8 Hz, 1H), 4.09-4.04 (m, 1H), 3.56 (dd, J = 4.5, 11.5 Hz, 1H), 2.12-1.96 (m, 2H), 1.89-1.60 (m, 8H), 1.52-1.42 (m, 1H), 1.09 (s, 3H), 1.05 (d, J = 7.6 Hz, 3H), 0.74 (s, 1H) ppm; 13C NMR (100 MHz, CDCl3) δ = 139.72, 139.32, 128.45, 128.31, 127.55, 127.47, 127.45, 127.32, 82.12, 78.91, 76.60, 71.89, 69.96, 45.71, 42.42, 32.81, 30.35, 26.26, 23.52, 19.05, 15.26, 10.33 ppm; IR (neat) 2939, 2867, 1496, 1453, 1386, 1364, 1095, 1071, 953, 735, 698 cm-1; HRMS (ESI) m/z Calcd for C26H34O3Na [M+Na]+: 417.2400, found 417.2390; Anal. Calcd for C26H34O3: C, 79.15; H, 8.69; found C, 78.96; H, 8.92.


To a stirred solution of compound 8 (18.3 g, 46.4 mmol) and pyridine (100 mL) in DCM (250 mL) at 0 °C was added a solution of SOCl2 (10 mL, 138 mmol) in DCM (50 mL) dropwise during 10 min. The reaction was stirred for 30 min at the same temperature and quenched with ice water (500 mL). The aqueous phase was extracted with DCM (300 mL), and the combined organic phase was washed with 5% HCl (300 mL) and brine (300 mL), dried over Na2SO4, evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 100:1-50:1) to afford 9 (16.1 g, 92%) as a colorless oil. 1H NMR (400 MHz, CDCl3) δ = 7.42-7.32 (m, 10H), 5.42 (brs, 1H), 4.75 (d, J = 11.9 Hz, 1H), 4.65 (d, J = 11.9 Hz, 1H), 4.54 (d, J = 12.1 Hz, 1H), 4.50 (d, J = 12.0 Hz, 1H), 3.50-3.45 (m, 1H), 3.19 (dd, J = 3.1, 12.2 Hz, 1H), 2.91-2.84 (m, 1H), 2.25-2.10 (m, 3H), 2.00-1.68 (m, 4H), 1.28 (s, 3H), 1.26 (d, J = 7.5 Hz, 3H), 1.15 (dt, J = 3.9, 13.5 Hz, 1H) ppm; 13C NMR (100 MHz, CDCl3) δ = 145.67, 139.42, 139.19, 128.39, 128.28, 127.47, 127.40, 127.34, 122.34, 85.61, 79.91, 71.20, 69.66, 41.55, 39.29, 36.53, 25.17, 23.19, 22.72, 20.64, 16.55 ppm; IR (neat) 2940, 2870, 1605, 1496, 1454, 1363, 1099, 1074, 1028, 734, 696 cm-1; HRMS (ESI) m/z Calcd for C26H32O2Na [M+Na]+: 399.2295, found 399.2286.


5


OBn

BnO

9

OBn

BnOHOH

9a

1) BH3.Me2S, Et2O,

RT, 20 h

2) NaOH, H2O2, THF,RT, 10 h

To a stirred solution of compound 9 (14.7 g, 39.1 mmol) in Et2O (400 mL) was added BH3•Me2S (neat, 8 mL, 80 mmol) dropwise during 10 min. The reaction was stirred for 20 h at rt, and then was added water/THF (1:1,100 mL) slowly at -10 °C. NaOH (3M, 100 mL) and 30% H2O2 (50 mL) were added successively, and the formed mixture was stirred for 10 h at rt. Cooled to 0 °C, saturated Na2S2O3 was added dropwise during 30 min, and the stirring continued for 30 min. The aqueous phase was extracted with Et2O (300 mL), and the combined organic phase was washed with saturated NH4Cl (300 mL) and brine (300 mL), dried over Na2SO4, evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 5:1) to afford 9a (12.6 g, 82%) as a colorless oil. 1H NMR (400 MHz, CDCl3) δ = 7.38-7.28 (m, 10H), 4.63 (d, J = 11.8 Hz, 1H), 4.61 (d, J = 11.8 Hz, 1H), 4.48 (d, J = 11.9 Hz, 1H), 4.41 (d, J = 11.8 Hz, 1H), 3.82 (dt, J = 4.1, 10.4 Hz, 1H), 3.42-3.37 (m, 1H), 2.89 (dd, J = 4.0, 11.4 Hz, 1H), 2.69-2.65 (m, 1H), 2.13-2.09 (m, 1H), 2.04-2.00 (m, 1H), 1.95-1.91 (m, 1H), 1.74-1.68 (m, 2H), 1.57-1.47 (m, 2H), 1.33-1.23 (m, 1H), 1.07-1.04 (m, 2H), 1.03 (d, J = 7.4 Hz, 3H), 1.01 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ = 139.25, 139.17, 12844, 128.33, 127.58, 127.46, 86.88, 80.59, 71.49, 69.61, 66.96, 51.45, 39.43, 37.01, 34.23, 30.28, 24.97, 23.27, 14.72, 9.14 ppm; IR (neat) 2936, 2856, 1637, 1453, 1384, 1363, 1073, 1027, 735, 697 cm-1; HRMS (ESI) m/z Calcd for C26H34O3Na [M + Na]+: 417.2400, found 417.2391; Anal. Calcd for C26H34O3: C, 79.15; H, 8.69; found C, 78.61; H, 9.07.

Synthesis of compound 9b

OBn

BnO

OAcH

9b

OBn

BnOHOH

9a

Ac2O, Py, DMAP

DCM, RT, 1 h

To a stirred solution of compound 9a (12.6 g, 32 mmol), pyridine (3.5 mL) and DMAP (0.5 g) in DCM (50 mL) was added Ac2O (3.6 mL, 35 mmol) dropwise during 5 min at 0 °C. The reaction was stirred for 1 h at rt, and then was quenched with ice water (100 mL). The aqueous phase was extracted with DCM (100 mL), and the combined organic phase was washed with 5% HCl (100 mL x 2) and brine (100 mL x 2), dried over Na2SO4, evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 10:1) to afford 9b (13.8 g, 99%) as a white solid. mp 80.5-81.8 °C. 1H NMR (400 MHz, CDCl3) δ = 7.36-7.27 (m, 10H), 5.01 (dt, J = 4.8, 11.1 Hz, 1H), 4.61 (d, J = 12.2 Hz, 1H), 4.58 (d, J = 13.0 Hz, 1H), 4.51 (d, J = 11.9 Hz, 1H), 4.41 (d, J = 11.8 Hz, 1H), 3.41-3.36 (m, 1H), 2.90 (dd, J = 4.0 , 11.5 Hz, 1H), 2.44-2.40 (m, 1H), 2.21-2.16 (m, 1H), 2.08-2.03 (m, 1H), 2.05 (s, 3H), 1.95-1.91 (m, 1H), 1.76-1.66 (m, 2H), 1.62-1.51 (m, 1H), 1.35-1.21 (m, 2H), 1.09-1.01 (m, 1H),1.04 (s, 3H), 0.91 (d, J = 7.4 Hz, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ = 170.70,

6


139.21, 139.15, 128.45, 128.36, 127.54, 127.50, 86.46, 80.59, 71.49, 70.10, 69.86, 48.88, 39.75, 36.90, 30.84, 30.31, 24.69, 22.97, 21.35, 14.59, 9.13 ppm; IR (neat) 2940, 2861, 1735, 1454, 1365, 1244, 1098, 1075, 1027, 735, 698 cm-1; HRMS (ESI) m/z Calcd for C28H36O4Na [M + Na]+ 459.2506, found 459.2496; Anal. Calcd for C28H36O4: C, 77.03; H, 8.31; found C, 76.72; H, 8.14.


To a solution of compound 9b (18.5 g, 42.4 mmol) in EtOH (500 mL) was added Pd/C (10%, 2 g), and the reaction was stirred for 20 h at rt under an atmosphere of H2. The reaction mixture was filtered through Celite and washed with MeOH (500 mL), then concentrated and purified by a flash column (silica gel, Hex/EA = 2:1) to afford 10 (10.3 g, 95%) as a white solid. mp 168.7- 170.1 °C. The structure of 10 was confirmed by X-ray crystallographic results. 1H NMR (400 MHz, CDCl3) δ = 4.97 (dt, J = 4.8 Hz, 11.2 Hz, 1H), 3.71-3.66 (m, 1H), 3.21 (dd, J = 3.6, 11.3 Hz, 1H), 2.29-2.25 (m, 1H), 2.15-2.11 (m, 1H), 2.02 (s, 3H), 1.83 (td, J = 3.2, 13.2 Hz, 1H), 1.74-1.70 (m, 1H), 1.66-1.63 (m, 2H), 1.45-1.28 (m, 4H), 1.18-1.10 (m, 1H), 0.94 (s, 3H), 0.87 (d, J = 7.4 Hz, 3H) ppm; 13C NMR (100MHz, CDCl3) δ = 170.75, 79.26, 73.69, 69.79, 48.57, 38.93, 36.53, 33.64, 30.32, 28.62, 25.69, 21.28, 13.45, 8.59 ppm; IR (neat) 2931, 2869, 1735, 1712, 1639, 1242, 1057, 1015 cm-1; HRMS (ESI) m/z Calcd for C14H24O4Na [M + Na]+ 279.1567, found 279.1569; Anal. Calcd for C14H24O4: C, 65.60; H, 9.44; found C, 65.39; H, 9.30.


To a stirred solution of compound 10 (9.6 g, 37.5 mmol) in acetone (400 mL) at 0 °C was added Jones’ reagent dropwise [prepared from CrO3 (27 g) and conc. H2SO4 (23 mL), and diluted to 100 mL with water] until TLC indicated the starting material was consumed completely. The reaction was quenched with iPrOH (10 mL) and filtered through Celite. The filtered cake was washed with acetone (400 mL). After concentration, the residue was partitioned between DCM (500 mL) and water (300 mL). The aqueous phase was extracted with DCM (200 mL x 2). The combined organic phase was washed with saturated NaHCO3 (200 mL ) and brine (200 mL), dried over Na2SO4, evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 6:1-3:1) to afford 10a (8.7 g, 92%) as a colorless oil, and revealed by 1H NMR a mixture of the C-4 methyl diastereomers with a α/β ratio of 7:3. mp 61.4-65.2 °C. 1H NMR (400 MHz, CDCl3) δ = 5.36 (dt, J = 4.5, 11.0 Hz,

7


0.7H), 5.18 (td, J = 5.6, 9.4 Hz, 0.3H), 2.83-2.33 (m, 6H), 2.19-1.74 (m, 6H), 1.65-1.58 (m, 1H), 1.40 (s, 1.93 H), 1.31 (s, 0.85H), 1.16 (d, J = 7.8 Hz, 1.93 H), 1.09 (d, J = 6.8 Hz, 0.85 H) ppm; 13C NMR (100 MHz, CDCl3) δ = 213.16, 211.24, 170.60, 71.80, 67.99, 50.68, 48.68, 46.61, 46.28, 45.02, 44.28, 36.02, 35.18, 34.52, 34.05, 32.49, 30.79, 29.39, 21.57, 21.12, 19.20, 17.84, 14.07 ppm; IR (neat) 2954, 1736, 1711, 1458, 1429, 1379, 1241, 1062, 1030 cm-1; HRMS (EI) m/z Calcd for C14H20O4 [M]+ 252.1356, found 252.1345; Anal. Calcd for C14H20O4: C, 66.65; H, 7.99; found C, 66.23; H, 7.81.


To a stirred solution of compound 10a (7.8 g, 31 mmol) in EtOH (150 mL) was added CH(OEt)3 (3.5 mL, 21 mmol) and pTsOH•H2O (150 mg, 0.8 mmol). The reaction was stirred for 30 min at rt, and then quenched with saturated NaHCO3 (150 mL), extracted with DCM (300 mL x 2). The combined organic phase was washed with brine (200 mL x 2), dried over Na2SO4, and evaporated to give a residue, which was purified by flash column (silica gel, Hex/EA = 10:1-5:1) to afford 11 (6.2 g, 61%, 90% brsm) as a white solid, and recovered dione (2.5 g, 32%). mp 83.5-85.0 °C. 1H NMR (400 MHz, CDCl3) δ = 5.27 (dt, J = 4.7, 11.1 Hz, 1H), 3.44-3.32 (m, 4H), 2.67 (dt, J = 6.7, 14.6, 1H), 2.35-2.19 (m, 3H), 2.08 (dd, J = 4.5, 11.9, 1H), 2.04 (s, 3H), 1.86-1.42 (m, 5H), 1.17 (s, 3H), 1.12 (t, J = 6.6 Hz, 6H), 0.92 (d, J = 7.5 Hz, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ = 212.79, 170.71, 101.82, 68.76, 54.92, 54.70, 47.04, 45.75, 35.35, 35.25, 30.93, 29.53, 23.91, 21.23, 19.68, 15.39, 15.29, 11.48 ppm; IR (neat) 2974, 1738, 1714, 1639, 1378, 1238, 1097, 1048, 1033 cm-1; HRMS (EI) m/z Calcd for C18H30O5 [M]+ 326.2088, found 326.2090; Anal. Calcd for C18H30O5: C, 66.23; H, 9.26; found C, 66.29; H, 9.39.


To a solution of compound 11 (7.9 g, 24.2 mmol) in MeOH (200 mL) was added K2CO3 (2 g), and the formed mixture was stirred for 4 h at rt. The reaction was quenched with saturated NH4Cl (100 mL), and extracted with DCM (250 mL x 3). The combined organic phase was washed with brine (100 mL), dried over Na2SO4, and evaporated under vacuum to give 11a as white solid, which was dissolved in EtOH (30 mL), and then was added dropwise to a stirred solution of hydrazine monohydrate (20 mL) and Et3N (20 mL) in EtOH (10 mL). The solution was stirred under reflux for 3 h. After evaporation, the residue was partitioned between EA (200

8


mL) and water (50 mL), and the aqueous phase was extracted with EA (100 mL x 3). The combined organic phase was washed with brine (50 mL), dried over Na2SO4, evaporated and dried under vacuum to give the hydrazone as a white solid, which was then used directly for the next process. To a stirred solution of I2 (19 g, 75 mmol) in THF (80 mL) was added a solution of TMG (1,1,3,3-tetramethylguanidine) (20 mL, 160 mmol) in THF (80 mL) dropwise during 30 min at rt, and then a solution of the above hydrazone in THF (80 mL) was added dropwise during 10 min. The reaction was stirred at rt for 10 min, cooled and quenched with saturated Na2S2O3 (100 mL), partitioned between EA (300 mL) and water (100 mL). The aqueous phase was extracted with EA (200 mL), and the combined organic phase was washed with brine (100 mL x 2), dried over Na2SO4, evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA/Et3N = 20:1:0.01) to afford 12 (8.0 g, 84%) as a pale yellow syrup. 1H NMR (400 MHz, C6D6) δ = 5.89 (dd, J = 2.8, 5.1 Hz, 1H), 3.58 (brs, 1H ), 3.43-3.35 (m, 3H), 3.21-3.17 (m, 1H), 2.57-2.54 (m, 1H), 2.19 (dd, J = 4.4, 11.6, 1H), 2.01-1.93 (m, 1H), 1.74-1.71 (m, 1H), 1.63-1.55 (m, 3H), 1.51-1.47 (m, 1H), 1.11 (t, J = 7.1 Hz, 3H), 1.05 (t, J = 7.0 Hz, 3H), 0.94-0.92 (m, 6H) ppm; 13C NMR (100 MHz, C6D6) δ = 134.71, 117.85, 102.88, 64.39, 55.05, 54.95, 48.15, 42.99, 40.98, 39.90, 34.68, 25.66, 20.80, 15.57, 15.52, 11.52 ppm; IR (neat) 2971, 2926, 1645, 1634, 1449, 1385, 1086, 1049 cm-1; HRMS (EI) m/z Calcd for C16H27IO3 [M]+ 394.0999, found 394.0986.


OHH

I

12

EtO

EtO

1) BnBr, NaH,DMF, 0 oC~r.t, 20 h

2) (CH2OH)2, pTsOH.H2O,

benzene, reflux, 20 hOBn

H

I

12a

O

O

To a stirred solution of compound 12 (4 g, 10 mmol) in DMF (40 mL) at 0 °C was added NaH (~60%, 2 g, 50 mmol) in portions. After stirring for 30 min, BnBr (3.5 mL, 29 mmol) was added dropwise during 5 min. The reaction was warmed up to rt and stirred for 20 h. Cooled to 0 °C, the reaction was quenched with water (40 mL), extracted with EA (100 mL x 2), washed with saturated NH4Cl (100 mL) and brine (100 mL), dried over Na2SO4, evaporated and dried under vacuum to give a residue, which was used directly for the next process. The residue above was dissolved in benzene (100 mL), followed by addition of ethylene glycol (4 mL) and pTsOH•H2O (400 mg, 2.1 mmol). The reaction was stirred under reflux for 20 h with the Dean-Stark apparatus to remove water formed, and then cooled to rt, partitioned between EA (100 mL) and water (100 mL). The organic phase was washed with saturated NaHCO3 (100 mL) and brine (100 mL), dried over Na2SO4, evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 50:1-30:1) to afford 12a (4.1 g, 89%) as a pale yellow semi-solid. 1H NMR (400 MHz, CDCl3) δ = 7.37-7.27 (m, 5H), 6.17 (dd, J = 2.8, 5.2 Hz, 1H), 4.64 (d, J = 11.4 Hz, 1H), 4.42 (d, J = 11.4 Hz, 1H), 3.97-3.88 (m, 4H), 3.77-3.70 (m, 1H), 2.66 (td, J = 5.6, 17.2 Hz, 1H), 2.32-2.26 (m, 2H), 2.12 (dq, J = 2.8, 8.8 Hz, 1H), 1.89-1.81 (m, 1H), 1.65-1.61 (m, 1H), 1.57-1.49 (m, 2H), 1.03 (s,

9


3H), 0.97 (d, J = 7.3 Hz, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ = 138.54, 134.05, 128.49, 127.86, 127.77, 117.25, 111.57, 71.36, 71.02, 64.48, 64.23, 47.58, 42.34, 40.20, 37.40, 36.15, 27.62, 20.72, 12.01 ppm; IR (neat) 2945, 2881, 1453, 1373, 1355, 1099, 736, 698 cm-1; HRMS (ESI) m/z Calcd for C21H28IO3 [M+H]+ 455.1078, found 455.1085.


A suspension of compound 12a (4.5 g, 10 mmol), Pd(OAc)2 (225 mg , 1 mmol) and Et3N (5.5 mL, 40 mmol) in MeOH/DMF (64 mL, 7/1) was degassed and charged with CO (balloon), stirred at 55 °C for 24 h. The reaction mixture was cooled to rt, diluted with EA (100 mL) and filtered through Cellite. The filtrate was washed with water (50 mL), saturated NH4Cl (50 mL) and brine (50 mL). The organic phase was collected, dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 50:1-20:1) to afford 13 (3.1 g, 81%) as a white solid. mp 99.5-100.2 °C. 1H NMR (400 MHz, CDCl3) δ = 7.35-7.27 (m, 5H), 6.59 (dd, J = 3.1, 4.6 Hz, 1H), 4.67 (d, J = 11.4 Hz, 1H), 4.45 (d, J = 11.4 Hz, 1H), 3.96-3.87 (m, 4H), 3.79-3.73 (m, 1H), 3.68 (s, 3H), 2.85 (td, J = 5.4, 18.9 Hz, 1H), 2.42-2.36 (m, 1H), 2.34-2.29 (m, 1H), 2.19 (dq, J = 3.0, 8.5 Hz, 1H), 2.03 (dd, J = 4.6, 11.5 Hz, 1H), 1.93 (ddd, J = 3.1, 4.1, 5.2 Hz, 1H ), 1.52-1.44 (m, 2H), 1.27 (s, 3H), 1.02 (d, J = 7.5 Hz, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ = 167.28, 140.62, 138.67, 135.19, 128.50, 127.86, 127.75, 111.37, 71.41, 71.04, 64.39, 64.17, 51.38, 47.56, 38.05, 36.09, 33.89, 33.09, 27.05, 21.20, 12.18 ppm; IR (neat) 2981, 2950, 2882, 1714, 1435, 1359, 1239, 1101, 1077, 737, 699 cm-1; HRMS (ESI) m/z Calcd for C23H31O5 [M+H]+ 387.2166, found 387.2163. Anal. Calcd for C23H30O5: C, 71.48; H, 7.82; found C, 71.49; H, 7.84.


To a solution of compound 13 (3 g, 7.8 mmol) in DCM (30 mL) at -78 °C was added DIBAL-H solution (15 mL, 1 M in toluene) dropwise during 5 min, and the reaction was stirred at the same temperature for 20 min. The reaction was quenched with saturated NH4Cl (20 mL), diluted with DCM (50 mL) and water (50 mL). The organic phase was washed with brine (50 mL x 2), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 2:1) to afford 13a (2.7 g, 97%) as a white solid. mp 109.7-110.7 °C. 1H NMR (400 MHz, CDCl3) δ = 7.35-7.27 (m, 5H), 5.54-5.52 (m, 1H), 4.67 (d, J = 11.4 Hz, 1H), 4.43 (d, J = 11.4

10


Hz, 1H), 4.13-4.06 (m, 2H), 3.97-3.88 (m, 4H), 3.81-3.74 (m, 1H), 2.81-2.74 (m, 1H), 2.40-2.33 (m, 1H), 2.13-2.05 (m, 2H), 1.92 (dt, J = 5.0, 13.3 Hz, 1H), 1.73-1.66 (m, 2H), 1.55-1.49 (m, 1H), 1.22 (brs, 1H), 1.13 (s, 3H), 1.01 (d, J = 7.5 Hz, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ = 146.33, 138.87, 128.45, 127.86, 127.64, 119.91, 111.49, 72.17, 70.75, 64.36, 64.18, 62.72, 47.19, 37.98, 36.15, 33.46, 33.25, 26.98, 21.93, 12.14 ppm; IR (neat) 2929, 2883, 1454, 1383, 1355, 1092, 988 cm-1; HRMS (ESI) m/z Calcd for C22H31O4 [M+H]+ 359.2217, found 359.2245. Anal. Calcd for C22H30O4: C, 73.71; H, 8.44; found C, 73.36; H, 8.96.


To a stirred solution of compound 13a (2.7 g, 7.5 mmol), DIPEA (6 mL, 36 mmol) and DMAP (10 mg) in toluene (50 mL) was added MOMCl (2.3 mL, 30 mmol) dropwise during 5 min at rt. The reaction was stirred at 70 °C for 20 h and then allowed to rt. The reaction was quenched with water (50 mL), extracted with EA (100 mL x 2), washed with saturated NaHCO3 (50 mL) and brine (50 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 20:1-10:1) to afford 14 (2.9 g, 96%) as a pale yellow oil. 1H NMR (400 MHz, CDCl3) δ = 7.35-7.28 (m, 5H), 5.55 (brs, 1H), 4.67 (d, J = 11.4 Hz, 1H), 4.61 (s, 2H), 4.42 (d, J = 11.4 Hz, 1H), 4.03 (d, J = 12.3 Hz, 1H), 3.96-3.88 (m, 5H), 3.81-3.75 (m, 1H), 3.36 (s, 3H), 2.77 (td, J = 5.5, 17.5 Hz, 1H), 2.39-2.33 (m, 1H), 2.12-2.05 (m, 2H), 1.92 (dt, J = 5.2, 13.0 Hz, 1H), 1.71-1.65 (m, 2H), 1.52 (dd, J = 1.7, 13.5 Hz, 1H), 1.10 (s, 3H), 1.01 (d, J = 7.5 Hz, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ = 142.70, 138.89, 128.43, 127.87, 127.62, 122.09, 111.51, 95.65, 72.11, 70.71, 67.20, 64.35, 64.18, 55.50, 47.15, 37.95, 36.13, 33.47, 33.36, 27.00, 21.69, 12.15 ppm; IR (neat) 2923, 2883, 1725, 1454, 1382, 1358, 1098, 698 cm-1; HRMS (ESI) m/z Calcd for C24H34O5Na [M+Na]+ 425.2298, found 425.2294.


To a stirred solution of compound 14 (2.6 g, 6.5 mmol) in Et2O (60 mL) was added BH3•Me2S (neat, 1.3 mL, 13 mmol) dropwise during 10 min. The reaction was stirred for 20 h at rt, and then was added water/THF (1:1, 20 mL) slowly at -10 °C. NaOH (3M, 20 mL) and 30% H2O2 (10 mL) were added successively, and the resultant mixture was stirred for 10 h at rt. Cooled to 0 °C, saturated Na2S2O3 was added dropwise during 30 min, and the stirring continued for additional 30 min. The aqueous phase was extracted with Et2O (100 mL), and the combined organic phase

11


was washed with saturated NH4Cl (100 mL) and brine (100 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 10:1-2:1) to afford 14a (2.1 g, 77%) as a colorless oil. 1H NMR (400 MHz, C6D6) δ = 7.32-7.30 (m, 2H), 7.18-7.15 (m, 2H), 7.10-7.06 (m, 1H), 4.53 (d, J = 11.4 Hz, 1H), 4.29 (s, 2H), 4.16 (d, J = 11.5 Hz, 1H), 3.87-3.80 (m, 1H), 3.70 (dd, J = 3.2, 9.9 Hz, 1H), 3.57-3.36 (m, 6H), 3.34 (d, J = 2.7 Hz, 1H), 3.09 (s, 3H), 2.77 (td, J = 4.6, 11.8 Hz, 1H), 2.68-2.61 (m, 1H), 2.05 (dd, J = 4.8, 11.2 Hz, 1H), 1.89 (ddd, J = 4.6, 4.1, 3.6 Hz, 1H), 1.65-1.46 (m, 4H), 1.39-1.34 (m, 1H), 1.12 (d, J = 7.6 Hz, 3H), 0.67 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 139.63, 128.54, 128.00, 127.59, 111.39, 96.65, 73.08, 70.53, 69.80, 67.78, 64.25, 64.08, 56.00, 55.18, 50.77, 41.60, 36.72, 36.39, 36.22, 27.14, 16.65, 12.55 ppm; IR (neat) 2934, 2884, 1453, 1386, 1148, 1101, 1030, 924, 698 cm-1; HRMS (ESI) m/z Calcd for C24H36O6Na [M+Na]+ 443.2404, found 443.2424.


To a stirred solution of compound 14a (2 g, 4.8 mmol), pyridine (1 mL) and DMAP (100 mg) in DCM (20 mL) was added Ac2O (0.7 mL, 7.1 mmol) at 0 °C. The reaction was warmed up to rt and stirred for 2 h, and then quenched with water (20 mL). The aqueous phase was extracted with DCM (50 mL), and the combined organic phase was washed with 5% HCl (50 mL) and brine (50 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 7:1-5:1) to afford 15 (2.1 g, 95%) as a white solid. mp 92.7-94.0 °C. 1H NMR (400 MHz, C6D6) δ = 7.30-7.28 (m, 2H), 7.18-7.14 (m, 2H), 7.09-7.06 (m, 1H), 5.27 (dt, J = 5.0, 11.5 Hz, 1H), 4.45-4.39 (m, 3H), 4.05 (d, J = 11.5 Hz, 1H), 3.58 (d, J = 3.5 Hz, 2H), 3.52-3.39 (m, 5H), 3.17 (s, 3H), 2.83 (td, J = 4.8, 11.3 Hz, 1H), 2.64-2.58 (m, 1H), 2.03 (dd, J = 4.8, 11.2 Hz, 1H), 1.95 (dt, J = 5.8, 12.6 Hz, 1H), 1.80 (s, 3H), 1.70-1.66 (m, 2H), 1.55-1.38 (m, 3H), 1.10 (d, J = 7.6 Hz, 3H), 0.90 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 169.94, 139.53, 128.55, 127.59, 111.41, 96.81, 73.07, 70.80, 69.61, 64.49, 64.24, 64.08, 55.03, 54.43, 50.74, 38.20, 36.78, 36.62, 36.52, 27.10, 20.94, 16.83, 12.36 ppm; IR (neat) 2946, 2885, 1733, 1369, 1245, 1149, 1101, 1029, 698 cm-1; HRMS (ESI) m/z Calcd for C26H38O7Na [M+Na]+ 485.2510, found 485.2517.

Synthesis of compound 15b

OBnH

15

O

O

MOMO

OAcMsCl, Et3N,Pd/C, H2,

EtOH,50 oC, 4 h OH

H

O

O

MOMO

OAc

15a

DCM,-78 oC, 40 min OMs

H

O

O

MOMO

OAc

15b To a solution of compound 15 (2 g, 4.3 mmol) in EtOH (50 mL) was added Pd/C (200

12


mg, 10%). The reaction was degassed and charged with H2 (balloon), stirred at 50 °C for 4 h. Cooled to rt, the reaction mixture was diluted with EA (200 mL), filtered through Celite. The filtrate was concentrated and the residue was dried under vacuum to give 15a as a colorless oil, which was used directly for the next process. To a stirred solution of compound 15a and Et3N (3 mL) in DCM (40 mL) was added MsCl (0.6 mL, 7.5 mmol) dropwise during 10 min at -78 °C. The reaction was stirred at the same temperature for 40 min, and then quenched with water (20 mL), extracted with DCM (30 mL x 2). The combined organic phase was washed with brine (40 mL x 2), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 7:1-5:1) to afford 15b (1.8 g, 92%) as a white solid. mp. 109.5-110.7 °C. 1H NMR (400 MHz, C6D6) δ = 5.15 (dt, J = 5.0, 11.5 Hz, 1H), 5.15 (dt, J = 5.1, 11.3 Hz, 1H), 4.37 (d, J = 6.4 Hz, 1H), 4.33 (d, J = 6.5 Hz, 1H), 3.50-3.44 (m, 6H), 3.12 (s, 3H), 2.99-2.94 (m, 1H), 2.32-2.30 (m, 1H), 2.27 (s, 3H), 2.01 (dd, J = 4.6, 11.6 Hz, 1H), 1.85-1.77 (m, 1H), 1.75 (s, 3H), 1.66-1.53 (m, 3H), 1.43-1.29 (m, 2H), 1.20 (d, J = 7.6 Hz, 3H), 0.65 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 169.69, 110.93, 96.68, 76.88, 68.60, 64.29, 64.17, 55.03, 53.99, 49.58, 39.50, 38.87, 36.87, 36.71, 36.38, 26.59, 20.76, 16.10, 12.06 ppm; IR (neat) 2944, 2879, 1735, 1451, 1342, 1244, 1174, 1150, 1100, 1032, 931, 903 cm-1; HRMS (ESI) m/z Calcd for C20H34O9SNa [M+Na]+ 473.1816, found 473.1810.


OMsH

MOMO

OAc

O

OMsH

O

O

MOMO

OAc

15b

PPTS, acetone/H2O,

reflux, 24 h

16

A solution of compound 15b (1.7 g, 3.8 mmol) and PPTS (100 mg, 0.4 mmol) in acetone/water (30 mL, 9/1) was stirred under reflux for 24 h. Cooled to rt, the reaction mixture was partitioned between EA (100mL) and water (50 mL), washed with saturated NaHCO3 (50 mL) and brine (50 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 3:2) to afford 16 (1.3 g, 85%) as a white solid. mp. 118.5-121.2 °C. 1H NMR (400 MHz, C6D6) δ = 5.07 (dt, J = 5.0, 11.5 Hz, 1H), 4.80 (dt, J = 5.1, 11.2 Hz, 1H), 4.34 (d, J = 6.4 Hz, 1H), 4.30 (d, J = 6.5 Hz, 1H), 3.38-3.31 (m, 2H), 3.11 (s, 3H), 3.05-2.99 (m, 1H), 2.76-2.69 (m, 1H), 2.20-2.11 (m, 1H), 2.15 (s, 3H), 2.03-1.99 (m, 1H), 1.72 (s, 3H), 1.60-1.53 (m, 2H), 1.34 (dd, J = 5.8, 11.4 Hz, 1H), 1.06 (d, J = 7.7 Hz, 3H), 1.03-0.95 (m, 2H), 0.50 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 210.87, 169.47, 96.72, 74.97, 68.07, 64.10, 55.11, 53.31, 50.75, 43.70, 39.32, 38.62, 37.96, 36.54, 33.80, 20.66, 15.50, 13.44 ppm; IR (neat) 2936, 2891, 1732, 1709, 1336, 1242, 1172, 1151, 1045, 931, 905 cm-1; HRMS (ESI) m/z Calcd for C18H30O8SNa [M+Na]+ 429.1554, found 429.1541; Anal. Calcd for C18H30O8S: C, 53.19; H, 7.44; found C, 53.55; H, 7.20.


13


OMsH

MOMO

OAc

O

OMsH

MOMO

OAc

O

1) PhSeCl, pTsOH.H2OEA, 0 oC, 2.5 h

2) Py, H2O2,DCM, 0 oC, 45 min

16a16

To a stirred solution of compound 16 (1.3 g, 3.2 mmol) in EA (35 mL) at 0 °C was added PhSeCl (0.6 g, 4.8 mmol) and pTsOH•H2O (67 mg, 0.35 mmol). The reaction was stirred at the same temperature for 2.5 h, and then diluted with DCM (35 mL), followed by addition of pyridine (1.5 mL) and H2O2 (30%, 1.5 mL). The stirring continued at 0 °C for 45 min, and aqueous CuSO4 (10%, 15 mL) was added. The resultant mixture was stirred for additional 10 min, diluted with water (50 mL), extracted with DCM (50 mL x 2). The combined organic phase was washed with saturated Na2S2O3 (50 mL), 5% HCl (50 mL) and brine (50 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 3:2) to afford 16a (0.92 g, 71%) as a white solid. mp 93.8-95.4 °C. 1H NMR (400 MHz, C6D6) δ = 6.77 (d, J = 10.4 Hz, 1H), 5.86 (d, J = 10.4 Hz, 1H), 4.97 (dt, J = 5.2, 11.4 Hz, 1H), 4.84 (dt, J = 5.1, 11.2 Hz, 1H), 4.33 (d, J = 6.5 Hz, 1H), 4.28 (d, J = 6.5 Hz, 1H), 3.41 (d, J = 4.2 Hz, 2H), 3.09 (s, 3H), 3.03-2.97 (m, 1H), 2.82-2.74 (m, 1H), 2.20 (s, 3H), 1.76-1.72 (m, 1H), 1.69 (s, 3H), 1.54-1.46 (m, 1H), 1.40-1.35 (m, 1H), 1.21 (d, J = 7.8 Hz, 3H), 0.57 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 199.81, 169.49, 154.48, 126.65, 96.60, 74.15, 67.79, 63.93, 55.20, 49.75, 48.92, 39.76, 39.19, 39.12, 38.47, 20.59, 17.64, 13.83 ppm; IR (neat) 2938, 2890, 1736, 1676, 1338, 1240, 1176, 1031, 936 cm-1; HRMS (ESI) m/z Calcd for C18H29O8S [M+H]+ 405.1578, found 405.1611; Anal. Calcd for C18H28O8S: C, 53.45; H, 6.98; found C, 53.74; H, 6.88.


OMsH

MOMO

OAc

O

516aOMs

H

MOMO

OH

O

K2CO3

MeOH, RT, 3 h

tBuOK, tBuOH,

70 oC, 15 min

OH

OMOM

O4

To a solution of compound 16a (800 mg, 2 mmol) in MeOH (20 mL) was added K2CO3 (200 mg). The reaction was stirred for 3 h at rt, and then partitioned between EA (50 mL) and water (20 mL), extracted with EA (20 mL x 2). The combined organic phase was washed with brine (20 mL), dried over Na2SO4, evaporated and dried under vacuum to give 5 as a white solid (700 mg, 98%), which was used directly for the next process. To a stirred solution of compound 5 in tBuOH (20 mL) was added tBuOK (2.4 g, 21 mmol) rapidly. The reaction was stirred at 70 °C for 15 min, and then cooled at an ice bath, quenched with saturated NH4Cl (20 mL), partitioned between EA (50 mL) and water (20 mL). The aqueous phase was extracted with EA (50 mL), and the combined organic phase was washed with brine (20 mL x 2), dried over Na2SO4, evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 3:1-2:1) to afford 4 (0.32 g, 61%) as a white semi-solid. 1H NMR (400 MHz, C6D6) δ = 6.33 (dd,

14


J = 1.8, 9.6 Hz, 1H), 6.04 (d, J = 9.6 Hz, 1H), 5.58 (td, J = 10.2, 16.7 Hz, 1H), 4.98-4.92 (m, 2H), 4.43 (s, 2H), 4.06 (brs, 1H), 3.58 (dd, J = 5.4, 10.0 Hz, 1H), 3.48-3.44 (m, 2H), 3.16 (s, 3H), 2.37 (d, J = 9.6 Hz, 1H), 2.06 (dd, J = 5.0, 9.1 Hz, 1H), 1.38 (s, 3H), 0.88 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 200.78, 158.44, 134.07, 128.34, 120.16, 96.93, 81.94, 67.80, 64.26, 60.89, 55.36, 54.86, 46.09, 18.67, 18.45 ppm; IR (neat) 2964, 2930, 1668, 1455, 1382, 1150, 1110, 1061, 919 cm-1; HRMS (ESI) m/z Calcd for C15H22O4Na [M+Na]+ 289.1410, found 289.1429.


To a solution of compound 4 (300 mg, 1.1 mmol) in DCM (15 mL) was added DMP (700 mg, 1.7 mmol). The reaction was stirred at rt for 40 min, and then was quenched with saturated Na2S2O3 (10 mL), extracted with DCM (20 mL x 2). The combined organic phase was washed with saturated NaHCO3 (20 mL) and brine (20 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 4:1) to afford 17 (268 mg, 90%) as a colorless oil. 1H NMR (400 MHz, C6D6) δ = 6.03 (dd, J = 2.2, 9.6 Hz, 1H), 5.72-5.62 (m, 2H), 5.05-4.99 (m, 2H), 4.21 (s, 2H), 3.80 (dd, J = 4.1, 10.1 Hz, 1H), 3.31 (dd, J = 2.4, 10.2 Hz, 1H), 3.11 (dd, J = 2.0, 9.4 Hz, 1H), 3.04 (s, 3H), 1.92 (dd, J = 2.4, 4.0 Hz, 1H), 1.45 (s, 3H), 0.94 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 210.67, 192.45, 157.85, 132.70, 127.06, 121.43, 96.51, 69.47, 65.25, 64.52, 55.28, 54.97, 44.01, 17.85, 13.79 ppm; IR (neat) 2932, 2884, 1747, 1681, 1450, 1373, 1151, 1112, 1033, 920 cm-1; HRMS (ESI) m/z Calcd for C15H20O4Na [M+Na]+ 287.1254, found 287.1254.


To a stirred solution of compound 17 (400 mg, 1.5 mmol) and CeCl3•7H2O (840 mg, 2.3 mmol) in MeOH (15 mL) at -78 °C was added NaBH4 (60 mg, 1.5 mmol) in portions during 15 min, and the stirring continued for 5 min at the same temperature. The reaction was quenched with saturated NH4Cl (10 mL), extracted with EA (30mL x 2). The combined organic phase was washed with brine (20 mL x 2), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 4:1-1:1) to afford 17a (181 mg, 45%) as a colorless oil. Other generated isomers were mixed and oxidized to the starting material diketone, which was used again for this reduction. After three recycles, the desired alcohol 17a (314 mg, total 78%) was obtained. 1H NMR (400 MHz, C6D6) δ = 6.17 (td, J = 9.9 , 17.1 Hz, 1H), 5.58 (dd, J = 3.7, 9.6 Hz, 1H), 5.46 (d, J = 9.5 Hz, 1H), 5.13 (dd, J = 2.2,

15


17.1 Hz, 1H), 5.06 (dd, J = 2.4 , 10.2 Hz, 1H), 4.25 (s, 2H), 3.74 (dd, J = 4.6, 10.0 Hz, 1H), 3.66-3.64 (m, 1H), 3.34 (dd, J = 2.5, 10.0 Hz, 1H), 3.08 (s, 3H), 2.82 (d, J = 9.7 Hz, 1H), 2.01 (dd, J = 2.5, 4.6 Hz, 1H), 1.41 (d, J = 7.2 Hz, 1H), 1.29 (s, 3H), 1.04 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 219.71, 140.82, 135.90, 127.82, 118.55, 96.49, 70.63, 65.68, 58.94, 57.10, 56.24, 55.18, 42.72, 18.37, 16.46 ppm; IR (neat) 2962, 2929, 2874, 1738, 1451, 1373, 1150, 1106, 1049, 1013, 917 cm-1; HRMS (ESI) m/z Calcd for C15H22O4Na [M+Na]+ 289.1410, found 289.1405.


To a stirred solution of compound 17a (330 mg, 1.2 mmol) and Et3N (0.7 mL, 5.0 mmol) in DCM (10 mL) at ice-salt bath was added TBSOTf (0.8 mL, 3.5 mmol) dropwise during 5 min. The reaction was allowed to warm to 0 °C and stirred under argon atmosphere for 3 h, and then quenched with saturated NaHCO3 (5 mL).The aqueous phase was extracted with DCM (20 mL), and the combined organic phase was washed with brine (20 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 40:1) to afford 18 (424 mg, 90%) as a colorless oil. 1H NMR (400 MHz, C6D6) δ = 6.40 (td, J = 10.3 , 16.6 Hz, 1H), 5.51 (s, 2H), 5.15 (dd, J = 2.3, 8.5 Hz, 1H), 5.12 (s, 1H), 4.28 (s, 2H), 3.83 (s, 1H), 3.78 (dd, J = 4.8, 10.0 Hz, 1H), 3.42 (dd, J = 2.4, 10.0 Hz, 1H), 3.11 (s, 3H), 2.85 (d, J = 10.0 Hz, 1H), 2.10 (dd, J = 2.4, 4.7 Hz, 1H), 1.34 (s, 3H), 1.11 (s, 3H), 0.94 (s, 9H), -0.01(s, 3H), -0.04 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 219.83, 140.49, 136.89, 127.82, 117.06, 96.56, 70.80, 65.75, 59.29, 57.18, 55.20, 42.87, 25.92, 18.48, 18.23, 17.34, 1.41, -4.35, -5.00 ppm; IR (neat) 2957, 2930, 2885, 2858, 1742, 1691, 1473, 1463, 1253, 1151, 1066, 883, 777 cm-1; HRMS (ESI) m/z Calcd for C21H36O4SiNa [M+Na]+ 403.2275, found 403.2297.


To a stirred mixture of Mg (192 mg, 8 mmol) and TiCl4 (0.21 mL, 2 mmol) in DCM (4 mL) at 0 °C was added a solution of compound 18 (380 mg, 1 mmol) in DCM/THF (3 mL/2 mL) dropwise during 2 min. The reaction was stirred for 45 min at 0 °C under argon atmosphere, and the resulting green-black mixture was stirred for additional 25 min at rt. The reaction mixture was re-cooled to 0 °C, and then quenched with saturated K2CO3 (2 mL), diluted with EA (50 mL), filtered through Celite. The filtrate was washed with saturated NaHCO3 (20 mL) and brine (20 mL), dried over Na2SO4, evaporated to give a residue, which was purified by a flash

16


column (silica gel, Hex/EA = 40:1-20:1) to afford 19 (291 mg, 77%) as a colorless oil. 1H NMR (400 MHz, C6D6) δ = 6.37 (td, J = 10.1, 17.0 Hz, 1H), 5.58 (s, 2H), 5.16-5.06 (m, 4H), 4.45 (s, 2H), 3.70 (s, 1H), 3.58 (dd, J = 6.8, 10.0 Hz, 1H), 3.43 (dd, J = 4.7, 10.2 Hz, 1H), 3.18 (s, 3H), 2.61-2.59 (m, 1H), 2.29 (d, J = 10.0 Hz, 1H), 1.29 (s, 3H), 1.14 (s, 3H), 0.99 (s, 9H), 0.06(s, 3H), 0.03 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 159.58, 139.47, 138.20, 127.82, 116.19, 110.00, 96.81, 75.73, 70.10, 58.28, 55.15, 54.76, 51.11, 44.54, 26.03, 21.40, 19.48, 18.29, -4.07, -4.88 ppm; IR (neat) 2956, 2929, 2858, 1635, 1251, 1151, 1112, 1064, 1042, 886, 836, 774 cm-1; HRMS (ESI) m/z Calcd for C22H38O3SiNa [M+Na]+ 401.2482, found 401.2501.


To a solution of compound 19 (240 mg, 0.63 mmol) in butanone/water (5mL/0.5 mL) was added NaI (286 mg, 1.9 mmol) and PPTS (240 mg, 0.95 mmol). The reaction was stirred under reflux for 20 h, and then cooled to rt, partitioned between EA (20 mL) and water (20 mL), extracted with EA (10 mL x 2). The combined organic phase was washed with saturated NaHCO3 (10 mL) and brine (10 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA =20:1-10:1) to afford 20 (119 mg, 56%) as a colorless oil. 1H NMR (400 MHz, C6D6) δ = 6.33 (td, J = 10.1, 17.0 Hz, 1H), 5.57-5.50 (m, 2H), 5.13-5.01 (m, 4H), 3.66 (d, J = 3.1 Hz, 1H), 3.51-3.45 (m, 1H), 3.33-3.28 (m, 1H), 2.35-2.32 (m, 1H), 2.21 (d, J = 10.0 Hz, 1H), 1.23 (s, 3H), 1.03 (s, 3H), 0.99 (s, 9H), 0.05(s, 3H), 0.02 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 159.48, 139.45, 138.04, 127.63, 116.23, 109.83, 75.78, 63.92, 58.26, 51.21, 44.45, 26.01, 21.26, 19.14, 18.28, -4.08, -4.90 ppm; IR (neat) 2957, 2929, 2857, 1635, 1251, 1060, 885, 836, 774 cm-1; HRMS (EI) m/z Calcd for C20H34O2Si [M]+ 334.2323, found 334.2324.


To a stirred solution of compound 20 (100 mg, 0.3 mmol) and VO(acac)2 (1.6 mg, 0.006 mmol) in benzene (3 mL) was added TBHP (5.5 M in decane, 66 μL, 0.36 mmol) at rt. The reaction was stirred for 4 h, and then diluted with EA (20 mL). The solution was washed with saturated NaHCO3 (10 mL) and brine (10 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA =15:1) to afford 21 (90 mg, 86%) as a colorless oil. 1H NMR (400 MHz, C6D6) δ = 6.20 (td, J = 10.1, 17.0 Hz, 1H), 5.50-5.43 (m, 2H), 5.08-5.00 (m, 2H), 3.71-3.65 (m, 1H), 3.53 (d, J = 3.4 Hz, 1H), 3.50-3.44 (m, 1H), 2.46 (dd, J = 5.6,

17


8.3 Hz, 1H), 2.41 (d, J = 10.0 Hz, 1H), 2.33 (d, J = 4.5 Hz, 1H), 2.28 (d, J = 4.5 Hz, 1H), 1.82 (dd, J = 3.9, 7.5 Hz, 1H), 0.95 (s, 9H), 0.94 (s, 3H), 0.93 (s, 3H), 0.01(s, 3H), -0.02 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 139.59, 137.32, 126.69, 116.77, 72.84, 69.17, 61.46, 58.10, 53.26, 48.67, 48.52, 44.15, 25.95, 19.09, 18.24, 16.09, -4.03, -4.97 ppm; IR (neat) 2958, 2929, 1635, 1256, 1063, 837, 774 cm-1; HRMS (ESI) m/z Calcd for C20H34O3SiNa [M+Na]+ 373.2169, found 373.2170.


To a stirred solution of compound 21 (80 mg, 0.23 mmol) in Et2O (8 mL) was added LAH (43 mg, 1.1 mmol) at rt. The reaction was stirred under reflux for 7 h. After being cooled to 0 °C, the reaction was quenched with Na2SO4•10 H2O (5 g) in portions and stirred for additional 2 h at rt, filtered. The filtered cake was washed with EA (10 mL x 3), and the combined filtrate was evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA =10:1-5:1) to afford 22 (72 mg, 90%) as a white solid. mp 91.0-92.0 °C. 1H NMR (400 MHz, C6D6) δ = 6.27 (td, J = 10.2, 16.9 Hz, 1H), 5.50 (dd, J = 3.6, 9.4 Hz, 1H), 5.45 (dd, J = 1.2, 9.6 Hz, 1H), 5.10-5.04 (m, 2H), 3.79 (d, J = 3.5 Hz, 1H), 3.64-3.58 (m, 1H), 3.55-3.50 (m, 1H), 2.48 (d, J = 10.1 Hz, 1H), 2.12 (s, 1H), 1.88 (t, J = 5.3 Hz, 1H), 1.62 (dd, J = 4.3, 9.0 Hz, 1H), 1.14 (s, 3H), 1.07 (s, 3H), 1.00 (s, 9H), 0.89 (s, 3H), 0.07 (s, 3H), 0.06 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 140.63, 138.50, 126.06, 115.91, 81.76, 70.47, 61.84, 59.31, 57.59, 53.59, 43.76, 42.48, 26.05, 19.27, 18.31, 16.14, -3.97, -4.88 ppm; IR (neat) 2958, 2929, 2857, 2886, 1462, 1374, 1253, 1048, 1022, 836, 774 cm-1; HRMS (ESI) m/z Calcd for C20H36O3SiNa [M+Na]+ 375.2326, found 375.2337.


To a solution of compound 22 (60 mg, 0.17 mmol) in DCM (9 mL) was added DMP (144 mg, 0.34 mmol) and NaHCO3 (71 mg, 0.85 mmol). The reaction was stirred at rt for 3 h, and then quenched with saturated NaHCO3 (10 mL), extracted with DCM (20 mL x 2). The combined organic phase was washed with NaHCO3 (20 mL) and brine (20 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 8:1) to afford 23 (53 mg, 88%) as a white solid. mp 108.5-109.7 °C. 1H NMR (400 MHz, C6D6) δ = 9.70 (d, J = 5.3 Hz, 1H), 6.18 (td, J = 10.1, 17.0 Hz, 1H), 5.39 (dd, J = 3.9, 9.4 Hz, 1H), 5.25(d, J = 9.4 Hz, 1H), 5.06 (dd, J = 2.4, 10.2 Hz, 1H), 5.02 (dd, J = 2.4, 17.1 Hz, 1H), 3.63 (d, J = 3.8 Hz, 1H), 2.69 (d, J = 10.0 Hz, 1H), 2.25 (d, J = 5.3 Hz, 1H), 1.07 (s, 1H), 0.96 (s, 12H), 0.89 (s,

18


3H), 0.86 (s, 3H), 0.01 (s, 3H), 0.00 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 201.08, 138.66, 137.20, 127.87, 116.59, 82.76, 70.05, 69.84, 58.40, 53.80, 44.50, 26.38, 25.97, 18.69, 18.24, 15.91, -4.06, -4.99 ppm; IR (neat) 2958, 2929, 2855, 1710, 1374, 1251, 1055, 881,772 cm-1; HRMS (ESI) m/z Calcd for C20H34O3SiNa [M+Na]+ 373.2169, found 373.2193.


To a stirred solution of compound 23 (25 mg, 0.071 mmol) in THF (5 mL) at 0 °C was added vinyl magnesium bromide (0.18 mL, 1M; freshly prepared following typical method) dropwise during 5 min. The reaction was stirred for 3 h at 0 °C under argon atmosphere, and then quenched with saturated NH4Cl (5 mL), extracted with EA (10 mL x 2). The combined organic phase was washed with saturated NaHCO3 (10 mL) and brine (10 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 10:1) to afford 24 (13 mg, 48%) as a white semi-solid. 1H NMR (400 MHz, C6D6) δ = 6.31 (td, J = 10.1, 17.0 Hz, 1H), 6.14-6.05 (m, 1H), 5.50 (s, 2H), 5.20-5.11 (m, 3H), 5.00 (td, J = 1.5, 10.4 Hz, 1H), 4.27-4.23 (m, 1H), 3.80 (d, J = 1.8 Hz, 1H), 2.96 (d, J = 8.2 Hz, 1H), 2.75 (d, J = 10.1 Hz, 1H), 2.22 (s, 1H), 1.62 (d, J = 3.3 Hz, 1H), 1.23 (s, 3H), 1.13 (s, 3H), 1.07 (s, 3H), 1.00 (s, 9H), 0.07 (s, 6H) ppm; 13C NMR (100 MHz, C6D6) δ = 143.20, 141.50, 138.74, 125.95, 84.35, 74.19, 70.44, 62.27, 58.11, 53.90, 44.91, 30.09, 27.20, 26.05, 25.98, 20.25, 18.31, 16.28, -3.96, -4.86 ppm; IR (neat) 2956, 2929, 2857, 1636, 1462, 1256, 1050, 836, 773 cm-1; HRMS (ESI) m/z Calcd for C22H38O3SiNa [M+Na]+ 401.2482, found 401.2492.


To a stirred mixture of Pd(OAc)2 (1 mg, 0.005 mmol) and CuCl2 (17 mg, 0.13 mmol) in THF (0.5 mL) was added 1,1,3,3-tetramethylthiourea (TMTU) (0.7 mg, 0.005 mmol) at rt, and the formed mixture was stirred for 30 min under argon atmosphere. To this solution was added propene oxide (PO) (0.018 mL, 0.25 mmol) and NH4OAc (4 mg, 0.005 mmol), and the mixture was purged with CO, followed by dropwise addition of enediol 24 (19 mg, 0.05 mmol) in THF (0.1 mL) during 2 min, and the reaction was stirred at 50 °C under CO atmosphere for 12 h. After being cooled to rt, the reaction mixture was diluted with EA (20 mL), filtered through Celite. The filtrate was washed with saturated NH4Cl (10 mL) and brine (10 mL), dried over Na2SO4,

19


and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 10:1-5:1) to afford 25 (16 mg, 78%) as a white semi-solid. 1H NMR (400 MHz, C6D6) δ = 6.22 (td, J = 10.0, 17.1 Hz, 1H), 5.53 (dd, J = 4.0, 9.5 Hz, 1H), 5.40 (d, J = 9.5 Hz, 1H), 5.22 (dd, J = 2.2, 17.1 Hz, 1H), 5.08 (dd, J = 2.4, 10.0 Hz, 1H), 3.90 (dd, J = 3.0, 6.6 Hz, 1H), 3.78 (d, J = 3.9 Hz, 1H), 3.65 (dd, J = 3.2, 4.4 Hz, 1H), 2.62 (d, J = 10.1 Hz, 1H), 2.28 (d, J = 17.6 Hz, 1H), 1.74 (dd, J = 4.5, 17.6 Hz, 1H), 1.59 (d, J = 6.6 Hz, 1H), 1.30 (s, 3H), 1.26 (s, 3H), 0.97 (s, 9H), 0.87 (s, 3H), 0.05 (s, 3H), 0.04 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 173.87, 139.66, 137.14, 126.86, 116.86, 94.71, 85.29, 78.10, 70.09, 62.78, 57.78, 51.87, 44.98, 34.51, 25.98, 20.64, 19.89, 18.29, 16.16, -3.98, -4.93 ppm; IR (neat) 2957, 2928, 2857, 1783, 1635, 1258, 1059, 774 cm-1; HRMS (ESI) m/z Calcd for C23H36O4SiNa [M+Na]+ 427.2275, found 427.2271.

Synthesis of compound 26 and 27

OTBS

OO

H

O

H

H

OTBS

OO

H

O

H

H

2) MsCl, Et3N, DMAPDCM, 35 oC, 40 h (A)/RT , 20 h (B)

+

OTBS

OO

H

O

H

H1) CH3CHO, LDA,THF, -78 oC, 3 h

25 26 27

To a solution of compound 25 (10 mg, 0.025 mmol) in THF (5 mL) was added LDA (0.15 mL, 1 M in THF, 0.15 mmol, freshly prepared following typical method) at -78 °C. The resultant mixture was stirred at the same temperature for 20 min, and acetaldehyde (10 μL, 0.17 mmol) was added. The reaction was stirred at -78 °C for 3 h, and then quenched with saturated NH4Cl (5 mL), extracted with EA (10 mL x 2). The combined organic phase was washed with saturated NaHCO3 (10 mL) and brine (10 mL), dried over Na2SO4, and evaporated to give a residue, which was subjected to the next process without further purification. Procedure A: To a solution of the above crude product in DCM (5 mL) was added Et3N (60 μL, 0.43 mmol), DMAP (1 mg) and MsCl (10 μL, 0.12 mmol). The resultant mixture was stirred at 35 °C for 40 h, and then quenched with saturated NH4Cl (5 mL), extracted with DCM (10 mL x 2). The combined organic phase was washed with saturated NaHCO3 (5 mL) and brine (5 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 8:1) to afford 26 (2.7 mg, 25% two steps) and 27 (6.5 mg, 61% two steps), both as a white semi-solid. Procedure B: To a solution of the above crude product in DCM (0.5 mL) was added Et3N (60 μL, 0.43 mmol), DMAP (1 mg) and MsCl (10 μL, 0.12 mmol). The resultant mixture was stirred at rt for 20 h, and then quenched with saturated NH4Cl (5 mL), extracted with DCM (10 mL x 2). The combined organic phase was washed with saturated NaHCO3 (5 mL) and brine (5 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 8:1) to afford 26 (5.5 mg, 52% two steps) and 27 (3.2 mg, 30% two steps).

20


Compound 26: 1H NMR (400 MHz, C6D6) δ = 6.23 (td, J = 10.1, 17.1 Hz, 1H), 5.96 (q, J = 7.2 Hz, 1H), 5.54 (dd, J = 3.9, 9.5 Hz, 1H), 5.42 (d, J = 9.5 Hz, 1H), 5.19 (dd, J = 2.1, 17.0 Hz, 1H), 5.06 (dd, J = 2.3, 10.1 Hz, 1H), 4.14 (d, J = 3.2 Hz, 1H), 4.06 (dd, J = 3.4, 6.8 Hz, 1H), 3.80 (d, J = 3.8 Hz, 1H), 2.71 (d, J = 10.1 Hz, 1H), 1.97 (d, J = 7.3 Hz, 3H), 1.71 (d, J = 6.8 Hz, 1H), 1.36 (s, 3H), 1.30 (s, 3H), 0.97 (s, 3H), 0.95 (s, 9H), 0.05 (s, 3H), 0.02 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 167.84, 142.69, 139.78, 137.17, 127.16, 126.78, 116.80, 95.33, 83.55, 81.26, 70.14, 62.91, 57.84, 52.01, 45.16, 25.98, 21.09, 20.09, 18.28, 16.25, 14.14, -3.99, -4.93 ppm; IR (neat) 2957, 2929, 2857, 1761, 1686, 1258, 1130, 1117, 1053, 869, 837 cm-1; HRMS (ESI) m/z Calcd for C25H38O4SiNa [M+Na]+ 453.2432, found 453.2430. Compound 27: 1H NMR (400 MHz, C6D6) δ = 6.72 (dq, J = 0.9, 7.2 Hz, 1H), 6.22 (td, J = 10.0, 17.1 Hz, 1H), 5.54 (dd, J = 4.0, 9.5 Hz, 1H), 5.43 (d, J = 9.4 Hz, 1H), 5.16 (dd, J = 2.2, 17.0 Hz, 1H), 5.05 (dd, J = 2.4, 10.0 Hz, 1H), 4.39 (d, J = 3.0 Hz, 1H), 4.08 (dd, J = 3.7, 7.1 Hz, 1H), 3.79 (d, J = 3.9 Hz, 1H), 2.64 (d, J = 10.2 Hz, 1H), 1.75 (d, J = 7.1 Hz, 1H), 1.41 (d, J = 7.2 Hz, 3H), 1.38 (s, 3H), 1.26 (s, 3H), 0.96 (s, 3H), 0.95 (s, 9H), 0.05 (s, 3H), 0.02 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 168.66, 139.78, 139.74, 137.09, 128.71, 126.77, 116.83, 95.79, 84.02, 76.69, 70.08, 62.75, 57.90, 51.99, 45.18, 25.97, 21.23, 20.18, 18.27, 16.29, 15.39, -4.01, -4.95 ppm; IR (neat) 2957, 2929, 2857, 1766, 1693, 1056, 773 cm-1; HRMS (ESI) m/z Calcd for C25H38O4SiNa [M+Na]+ 453.2432, found 453.2430.


To a solution of compound 26 (5 mg, 0.012 mmol) in CH3CN (1 mL) was added aqueous HF (aq. 40%, 0.2 mL). The reaction was stirred at rt for 20 h, and then quenched with saturated NaHCO3 (2 mL), extracted with EA (5 mL x 2). The combined organic phase was washed with brine (5 mL x 2), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 3:1) to afford 26a (3.3 mg, 90%) as a white semi-solid. 1H NMR (400 MHz, C6D6) δ = 5.97-5.82 (m, 2H), 5.59 (dd, J = 4.0, 9.5 Hz, 1H), 5.35 (d, J = 9.4 Hz, 1H), 5.12 (dd, J = 1.4, 17.1 Hz, 1H), 4.96 (dd, J = 2.0, 10.3 Hz, 1H), 4.07 (d, J = 3.3 Hz, 1H), 4.00 (dd, J = 3.4, 6.8 Hz, 1H), 3.58-3.55 (m, 1H), 2.66 (d, J = 9.5 Hz, 1H), 1.98 (d, J = 7.3 Hz, 3H), 1.64 (d, J = 6.7 Hz, 1H), 1.28 (s, 3H), 1.26 (s, 3H), 1.15 (d, J = 8.3 Hz, 1H), 0.84 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 167.82, 142.68, 139.74, 135.62, 127.37, 127.14, 119.13, 95.30, 83.53, 81.15, 69.90, 62.74, 56.30, 51.96, 45.01, 20.85, 19.98, 15.43, 14.13 ppm; IR (neat) 2961, 2925, 1755, 1684, 1374, 1215, 1131, 1031, 1011, 965 cm-1; HRMS (ESI) m/z Calcd for C19H24O4Na [M+Na]+ 339.1567, found 339.1568.

21


Synthesis of pallambin C (1)

To a solution of compound 26a (3 mg, 0.0095 mmol) in DCM (0.5 mL) was added DMP (8 mg, 0.019 mmol) and NaHCO3 (4 mg, 0.048 mmol). The reaction was stirred at rt for 1 h, and then quenched with saturated Na2S2O3 (2 mL), extracted with DCM (5 mL x 2). The combined organic phase was washed with aqueous NaHCO3 (5 mL) and brine (5 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 3:1) to afford 1 (2.8 mg, 95%) as a colorless oil. 1H NMR (400 MHz, CDCl3) δ = 6.71-6.66 (m, 2H), 5.89 (d, J = 9.6 Hz, 1H), 5.54 (td, J = 9.8, 16.9 Hz, 1H), 5.22-5.15 (m, 2H), 4.88 (dd, J = 3.2, 6.7 Hz, 1H), 4.84 (d, J = 3.2 Hz, 1H), 2.83 (dd, J = 1.6, 9.5 Hz, 1H), 2.53 (d, J = 6.7 Hz, 1H), 2.25 (d, J = 7.3 Hz, 3H), 1.42 (s, 3H), 1.14 (s, 3H), 1.04 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ = 201.56, 168.38, 157.11, 144.82, 132.39, 127.01, 126.10, 121.78, 94.17, 83.13, 82.34, 63.98, 62.79, 60.83, 47.02, 22.43, 19.68, 14.60, 12.88 ppm; IR (neat) 2967, 2929, 1759, 1681, 1375, 1118, 916 cm-1; HRMS (ESI) m/z Calcd for C19H23O4 [M+H]+ 315.1591, found 315.1606.


To a solution of compound 27 (5 mg, 0.012 mmol) in CH3CN (1 mL) was added aqueous HF (aq. 40%, 0.2 mL). The reaction was stirred at rt for 20 h, and then quenched with saturated NaHCO3 (2 mL), extracted with EA (5 mL x 2). The combined organic phase was washed with brine (5 mL x 2), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 3:1) to afford 27a (3.3 mg, 90%) as a white semi-solid. 1H NMR (400 MHz, C6D6) δ = 6.72 (q, J = 7.2 Hz, 1H), 5.86 (td, J = 9.9, 17.2 Hz, 1H), 5.59 (dd, J = 4.0, 9.4 Hz, 1H), 5.35 (d, J = 9.4 Hz, 1H), 5.09 (dd, J = 1.4, 17.2 Hz, 1H), 4.95 (dd, J = 1.9, 10.2 Hz, 1H), 4.32 (d, J = 3.1 Hz, 1H), 4.02 (dd, J = 3.6, 7.0 Hz, 1H), 3.55-3.52 (m, 1H), 2.61 (d, J = 9.4 Hz, 1H), 1.67 (d, J = 7.0 Hz, 1H), 1.39 (d, J = 7.2 Hz, 3H), 1.31 (s, 3H), 1.23 (s, 3H), 1.15 (d, J = 8.3 Hz, 1H), 0.83 (s, 3H) ppm; 13C NMR (100 MHz, C6D6) δ = 168.64, 139.75, 135.56, 128.68, 127.33, 119.11, 95.78, 84.00, 76.58, 69.84, 62.57, 56.37, 51.94, 45.02, 20.97, 20.07, 15.48, 15.40 ppm; IR (neat) 2956, 2927, 1756, 1693, 1375, 1217, 1143, 1074, 1031, 738 cm-1; HRMS (ESI) m/z Calcd

22


for C19H24O4Na [M+Na]+ 339.1567, found 339.1568.

Synthesis of pallambin D (2)

To a solution of compound 27a (3 mg, 0.0095 mmol) in DCM (0.5 mL) was added DMP (8 mg, 0.019 mmol) and (4 mg, 0.048 mmol). The reaction was stirred at rt for 2 h, and then quenched with saturated Na2S2O3 (2 mL), extracted with DCM (5 mL x 2). The combined organic phase was washed with aqueous NaHCO3 (5 mL) and brine (5 mL), dried over Na2SO4, and evaporated to give a residue, which was purified by a flash column (silica gel, Hex/EA = 3:1) to afford 2 (2.6 mg, 89%) as a white solid. mp 184.5-185.7 °C (lit.[1] mp 191 °C). 1H NMR (400 MHz, CDCl3) δ = 7.00 (q, J = 7.3 Hz, 1H), 6.69 (dd, J = 1.9, 9.5 Hz, 1H), 5.89 (d, J = 9.6 Hz, 1H), 5.53 (td, J = 9.8, 16.9 Hz, 1H), 5.20-5.15 (m, 2H), 5.09 (d, J = 3.2 Hz, 1H), 4.90 (dd, J = 3.6, 7.0 Hz, 1H), 2.76 (dd, J = 1.8, 9.4 Hz, 1H), 2.56 (d, J = 7.0 Hz, 1H), 2.03 (d, J = 7.2 Hz, 3H), 1.42 (s, 3H), 1.16 (s, 3H), 1.01 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ = 201.61, 169.53, 157.12, 141.89, 132.37, 127.68, 126.97, 121.73, 94.51, 83.80, 77.76, 64.03, 62.79, 60.62, 47.03, 22.50, 19.78, 16.18, 12.84 ppm; IR (neat) 2967, 2931, 1764, 1682, 1376, 1209, 1121, 1072, 973 cm-1; HRMS (ESI) m/z Calcd for C19H23O4 [M+H]+ 315.1591, found 315.1594. 1 M. Toyota, T. Sato, Y. Asakawa, Chem. Pharm. Bull. 1998, 46, 178 – 180.

23


Spectral comparison between natural and synthetic

Pallambin C (1):

H Natural (600M, CDCl3,

solvent signal 7.28, δ ppm)Synthetic (400M, CDCl3, solvent signal 7.26, δ ppm)

1 6.69 (m) 6.68 (m) 2 5.89 (d, 9.6) 5.89 (d, 9.6) 5 2.84 (dd, 9.9, 2.0) 2.83 (dd, 9.5, 1.6) 6 5.54 (dt, 17.0, 9.9) 5.54 (dt, 16.9, 9.8) 7 5.19 (2H, m) 5.18 (2H, m) 9 2.54 (d, 6.7) 2.53 (d, 6.7) 11 4.89 (dd, 6.8, 3.3) 4.88 (dd, 6.7, 3.2) 12 4.85 (d, 3.3) 4.84 (d, 3.2) 14 6.69 (1H, m) 6.67 (1H, m) 15 2.26 (3H, d, 7.3) 2.25 (3H, d, 7.3) 17 1.15 (3H, S) 1.14 (3H, S) 18 1.04 (3H, S) 1.04 (3H, S) 19 1.42 (3H, S) 1.42 (3H, S)

C Natural (150M, CDCl3, solvent signal 77.02, δ

ppm)

Synthetic (100M, CDCl3, solvent signal 77.16, δ

ppm) 1 156.9 157.1 2 126.8 127.0 3 201.3 201.6 4 62.6 62.8 5 63.8 64.0 6 132.2 132.4 7 121.5 121.8 8 94.0 94.2 9 60.6 60.8 10 46.8 47.0 11 82.9 83.1

24


12 82.1 82.3 13 125.9 126.1 14 144.6 144.8 15 14.4 14.6 16 168.1 168.4 17 22.2 22.4 18 12.7 12.9 19 19.5 19.7

Pallambin D (2):

O

OO

H

O

H

H

12

3

45

67

1789

1019 18

14

1211

13

15

16

H Natural (600M, CDCl3,

solvent signal 7.28, δ ppm)Synthetic (400M, CDCl3, solvent signal 7.26, δ ppm)

1 6.70 (dd, 9.6, 2.1) 6.69 (dd, 9.5, 1.9) 2 5.91 (d, 9.6) 5.89 (d, 9.6) 5 2.78 (dd, 9.9, 2.0) 2.76 (dd, 9.4, 1.8) 6 5.55 (dt, 16.9, 9.9) 5.53 (dt, 16.9, 9.8) 7 5.19 (2H, m) 5.17 (2H, m) 9 2.58 (d, 7.0) 2.56 (d, 7.0) 11 4.92 (dd, 7.0, 3.6) 4.90 (dd, 7.0, 3.6) 12 5.11 (dd, 3.5, 0.8) 5.09 (d, 3.2) 14 7.07 (qd, 7.2, 0.8) 7.00 (q, 7.3) 15 2.06 (3H, d, 7.2) 2.03 (3H, d, 7.2) 17 1.18 (3H, S) 1.16 (3H, S) 18 1.03 (3H, S) 1.01 (3H, S) 19 1.44 (3H, S) 1.42 (3H, S)

C Natural (150M, CDCl3, solvent signal 77.00, δ

ppm)

Synthetic (100M, CDCl3, solvent signal 77.16, δ

ppm) 1 157.0 157.1 2 126.8 127.0 3 201.3 201.6 4 62.7 62.8 5 63.9 64.0 6 132.2 132.4

25


7 121.5 121.7 8 94.4 94.5 9 60.3 60.6 10 46.7 47.0 11 83.6 83.8 12 77.6 77.8 13 127.5 127.7 14 141.7 141.9 15 16.0 16.2 16 169.3 169.5 17 22.3 22.5 18 12.7 12.8 19 19.6 19.8

26


Basic crystal data for compounds 2, 10, 11, 16 and 22 CCDC 879025 (2), CCDC 879026 (10), CCDC 879027 (11), CCDC 879028 (16) and CCDC 879029 (22) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. Chem. Commun. Deposition Number(s) 879025 879026 879027 879028 879029 CIF files for 5 structures are attached to this message. CCDC No Acell Bcell Ccell Space Gp. 879025 7.3712 8.0916 13.8262 P-1 879026 14.4194 14.4194 6.0541 P32 879027 8.3310 8.7830 13.7240 P-1 879028 14.7240 6.7900 22.3940 P21/n 879029 11.6292 7.7435 12.2967 P21

ORTEP diagram of compound 2. Thermal ellipsoids were plotted at 30 % probability level. Hydrogen atoms are omitted for clarity.

27




28




29


natu

ral

600 M

Hz in C

DC

L3

ppm

(t1)

1.0

2.0

3.0

4.0

5.0

6.0

synth

etic

400 M

Hz

in C

DC

l3

30


dell

图章

dell

图章

dell

附注

dell

附注

dell

附注

150M

Hz

in C

DC

l3

natu

ral

ppm

(t1)

5010

015

020

0

synth

etic

100 M

Hz

in C

DC

l3

31


dell

图章

dell

图章

600 M

Hz

in C

DC

l3

natu

ral

ppm

(f1)

1.0

2.0

3.0

4.0

5.0

6.0

7.0

synth

etic

400 M

Hz

in C

DC

l3

32


dell

图章

dell

图章

natu

ral

150 M

Hz

in C

DC

l3

ppm

(t1)

5010

015

020

0

synth

etic

100 M

Hz

in C

DC

l3

33


dell

图章

dell

图章

7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

1.0677

1.2274

1.2388

1.2514

1.2618

1.2725

1.2847

1.2955

1.3062

1.3178

1.3280

1.3383

1.4292

1.4404

1.4567

1.4764

1.5376

1.5474

1.5690

1.5783

1.5985

1.6031

1.6091

1.6272

1.7471

1.7519

1.7582

1.7640

1.7767

1.7817

1.8079

1.8199

1.8336

1.8469

1.8591

1.9326

1.9379

1.9427

1.9671

1.9771

1.9904

2.0075

2.0970

2.1029

2.1088

2.1317

2.1372

2.1432

2.1663

2.1716

2.1778

3.2388

3.2496

3.2619

3.2670

3.2785

3.2890

4.1750

4.1844

5.4097

7.2599

3.152

1.164

4.140

1.100

3.198

2.148

1.117

1.028

1.031

1.000

NAME XS-1-7-A1EXPNO 1PROCNO 1Date_ 20110919Time 18.50INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 6DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 101DW 60.800 usecDE 6.50 usecTE 298.9 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 14.00 usecPL1 -1.00 dBPL1W 13.56617069 WSFO1 400.1924713 MHzSI 32768SF 400.1900141 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00

Bruker Advance III 400

NAME XS-1-7-A1EXPNO 2PROCNO 1Date_ 20110919Time 18.57INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT CDCl3NS 176DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 299.3 KD1 2.00000000 secD11 0.03000000 secTD0 1

======== CHANNEL f1 ========NUC1 13CP1 9.90 usecPL1 -2.00 dBPL1W 55.33689499 WSFO1 100.6379183 MHz

======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 -1.00 dBPL12 15.16 dBPL13 18.62 dBPL2W 13.56617069 WPL12W 0.32844096 WPL13W 0.14806664 WSFO2 400.1916008 MHzSI 32768SF 100.6278427 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.916

24.709

28.998

30.851

31.464

33.636

40.762

67.787

76.843

77.160

77.478

79.217

126.055

144.917


34


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

1.1483

1.1716

1.1822

1.1924

1.2059

1.2159

1.2257

1.2393

1.2495

1.2594

1.3054

1.3178

1.3461

1.3804

1.5357

1.5643

1.5701

1.5818

1.5974

1.7926

1.8109

1.8211

1.9617

1.9851

1.9961

2.0235

2.0295

2.0422

2.1461

2.1516

2.1748

2.1800

2.1859

2.2092

2.9562

2.9666

2.9851

2.9955

3.9360

3.9468

3.9516

3.9654

4.4111

4.4408

4.5440

4.5739

4.6017

4.6314

4.6459

4.6756

5.4924

7.2597

7.2741

7.2852

7.2900

7.2945

7.3245

7.3384

7.3486

7.3605

7.3809

3.097

1.039

1.263

2.336

1.288

4.186

1.153

1.014

1.008

1.063

1.100

1.157

1.031

1.000

10.370

NAME XS-1-5-A1EXPNO 2PROCNO 1Date_ 20110923Time 17.03INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT CDCl3NS 5DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 50.8DW 60.800 usecDE 6.50 usecTE 299.4 KD1 1.00000000 secTD0 1






210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

17.994

24.633

25.349

26.744

31.780

34.067

41.126

70.049

71.437

74.484

76.843

77.160

77.478

86.455

123.386

127.448

127.536

127.561

127.812

128.350

128.453

139.140

139.396

145.593


35


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

0.9381

0.9741

1.1936

1.2443

1.2505

1.2800

1.3135

1.3195

1.4330

1.4412

1.4570

1.4658

1.4750

1.4905

1.4997

1.5103

1.5264

1.5347

1.5626

1.5716

1.5980

1.6056

1.6202

1.6393

1.6478

1.7346

1.7450

1.7577

1.8912

1.9009

1.9113

1.9338

1.9434

1.9780

1.9900

2.0123

2.0227

2.0439

3.0445

3.3278

3.3390

3.3546

3.3654

3.7015

3.7217

3.7252

3.7446

4.4217

4.4513

4.6327

4.6604

7.2591

7.2670

7.2782

7.2890

7.2997

7.3253

7.3358

7.3622

7.3683

7.3757

1.014

3.009

1.082

1.119

3.084

1.028

1.065

2.040

0.988

1.006

1.000

1.024

2.070

1.012

10.063







210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.251

20.744

24.071

26.476

27.556

29.139

38.883

61.533

66.622

71.320

71.677

72.701

76.845

77.162

77.480

83.692

127.461

127.528

127.863

128.351

128.578

138.331

139.313


36


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

1.0630

1.0933

1.4175

1.4301

1.4503

1.4624

1.4810

1.4929

1.5122

1.5247

1.6033

1.6214

1.6283

1.6424

1.6500

1.6620

1.6687

1.6792

1.6924

1.7092

1.7145

1.7264

1.7378

1.7445

1.7597

1.7720

1.7940

1.8112

1.8215

1.8626

1.8802

1.8944

1.9628

1.9812

1.9984

2.0149

2.0334

2.0482

2.0558

2.0610

2.0819

2.0950

2.1155

2.1287

3.5375

3.5488

3.5663

3.5776

4.0372

4.0504

4.0642

4.0777

4.0912

4.4243

4.4538

4.4774

4.5071

4.5399

4.5696

4.5906

4.6200

5.2948

7.2600

7.2711

7.2805

7.2883

7.3263

7.3374

7.3576

7.3725

0.942

3.208

3.159

1.088

7.950

2.114

1.000

1.045

1.014

1.011

1.041

0.973

10.559







210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

10.328

15.259

19.052

23.524

26.259

30.354

32.806

42.417

45.709

69.958

71.887

76.596

76.842

77.160

77.478

78.907

82.122

127.321

127.451

127.470

127.549

128.310

128.452

139.318

139.716


37


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

4.4858

4.5158

4.5208

4.5510

1.1136

1.1229

1.1473

1.1571

1.1811

1.1908

1.2524

1.2711

1.2820

1.6794

1.6942

1.7065

1.7243

1.7356

1.7533

1.7656

1.7837

1.7956

1.8050

1.8178

1.8282

1.8375

1.8500

1.8595

1.8872

1.9142

1.9219

1.9565

1.9655

1.9727

1.9973

2.0968

2.1074

2.1364

2.1419

2.1644

2.1737

2.1896

2.1979

2.2351

2.2479

2.8389

2.8565

2.8732

2.8899

2.9074

3.1666

3.1744

3.1970

3.2048

3.4509

3.4633

3.4784

3.4923

3.5043

4.6358

4.6656

4.7302

4.7599

5.4223

7.2603

7.3162

7.3327

7.3488

7.3852

7.4037

7.4189

1.171

2.981

2.979

4.336

3.100

1.008

1.004

1.009

0.988

1.034

1.043

1.024

1.000

10.226







210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

16.549

20.639

22.721

23.185

25.168

36.525

39.288

41.551

69.658

71.195

76.841

77.160

77.478

79.908

85.611

122.337

127.340

127.397

127.471

128.276

128.387

139.194

139.416

145.665


38


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

3.7915

3.8533

1.0063

1.0204

1.0388

1.0636

1.0749

1.2283

1.2394

1.2619

1.2956

1.3212

1.3321

1.4709

1.5007

1.5303

1.5394

1.5638

1.5739

1.6877

1.7160

1.7242

1.7349

1.7440

1.9062

1.9139

1.9255

1.9388

1.9467

2.0044

2.0125

2.0305

2.0379

2.0875

2.0957

2.1071

2.1186

2.1266

2.6529

2.6650

2.6827

2.6947

2.7128

2.8677

2.8777

2.8963

2.9063

3.3692

3.3838

3.4012

3.4087

3.4223

3.8020

3.8171

3.8273

3.8427

4.3997

4.4293

4.4611

4.4909

4.5999

4.6185

4.6293

4.6481

7.2600

7.2793

7.2954

7.3315

7.3481

7.3660

7.3824

3.115

3.179

1.989

1.123

2.042

2.274

1.008

0.987

0.985

1.007

0.999

1.003

1.000

0.968

0.982

2.048

10.102







210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

9.142

14.715

23.274

24.971

30.284

34.228

37.008

39.426

51.453

66.960

69.608

71.493

76.845

77.163

77.481

80.592

86.884

127.461

127.575

128.330

128.437

139.170

139.252


39


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

1.2516

1.2756

1.3023

1.3138

1.3244

1.3426

1.3533

1.5096

1.5201

1.5438

1.5494

1.5533

1.5728

1.5828

1.6070

1.6178

1.6310

1.6593

1.6673

1.6918

1.6966

1.7194

1.7286

1.7395

1.7518

1.7609

1.9097

1.9171

1.9285

1.9428

1.9505

2.0262

2.0351

2.0538

2.0834

2.1635

2.1712

2.1828

2.1946

2.2023

2.2131

2.3994

2.4116

2.4293

2.4411

2.8771

2.8873

2.9059

2.9160

3.3608

3.3732

3.3864

3.4012

3.4137

4.3909

4.4204

4.4935

4.5233

4.5662

4.5987

4.6291

4.9763

4.9882

5.0039

5.0160

5.0317

5.0437

7.2603

7.2731

7.2773

7.2866

7.2933

7.2991

7.3065

7.3233

7.3404

7.3456

7.3616

3.094

3.001

0.892

2.153

1.090

2.008

1.095

1.066

3.013

1.081

1.023

1.000

1.008

0.986

0.978

1.035

0.947

1.020

10.333







210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

9.134

14.590

21.347

22.972

24.692

30.307

30.837

36.898

39.745

48.877

69.860

70.102

71.487

76.841

77.159

77.477

80.594

86.457

127.500

127.536

128.362

128.448

139.148

139.207

170.700


40


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.8600

0.8786

0.9431

1.1021

1.1237

1.1349

1.1468

1.1785

1.3140

1.3260

1.3450

1.3552

1.3736

1.3846

1.4134

1.4490

1.5419

1.5525

1.5754

1.5856

1.6157

1.6304

1.6389

1.6524

1.6612

1.7029

1.7098

1.7222

1.7358

1.7430

1.8015

1.8094

1.8179

1.8344

1.8427

1.8505

2.0237

2.1107

2.1180

2.1301

2.1420

2.1488

2.2450

2.2573

2.2750

2.2868

3.1899

3.1992

3.2185

3.2273

3.6594

3.6747

3.6864

3.6969

3.7108

4.9400

4.9518

4.9678

4.9799

4.9956

5.0075

7.2601

3.014

3.049

1.172

4.012

1.292

2.041

1.085

1.095

3.017

1.099

1.033

1.023

1.039

1.000







210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

8.589

13.446

21.280

25.687

28.616

30.320

33.639

36.525

38.929

48.568

69.790

73.691

76.842

77.160

77.477

79.263

170.751


41


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

1.0766

1.0935

1.1515

1.1709

1.3149

1.3965

1.6122

1.6164

1.6195

1.6247

1.6292

1.6386

1.6425

1.6484

1.6509

1.6555

1.6609

1.6743

1.6965

1.7758

1.7913

1.7984

1.8040

1.8110

1.8258

1.8888

1.9119

1.9245

1.9469

1.9594

1.9698

1.9769

1.9860

1.9936

2.0085

2.0127

2.0221

2.0303

2.0471

2.0526

2.0994

2.1061

2.1080

2.1138

2.1235

2.1352

2.1428

2.1572

2.1716

2.1859

2.3275

2.3337

2.3370

2.3404

2.3456

2.3581

2.3647

2.3719

2.3773

2.3804

2.3839

2.3923

2.3994

2.4128

2.4153

2.4266

2.4343

2.4435

2.4472

2.4542

2.4656

2.4736

2.5432

2.5597

2.5763

2.5885

2.5937

2.5996

2.6104

2.6155

2.6231

2.6269

2.6334

2.6500

2.6857

2.7042

2.7229

2.7380

2.7542

2.7746

2.7908

2.8111

2.8271

5.1701

5.1935

5.3219

5.3339

5.3493

5.3613

5.3770

5.3888

7.2600

0.849

1.934

0.854

1.929

1.298

6.441

6.193

0.301

0.699

NAME XS-1-6-A1EXPNO 2PROCNO 1Date_ 20111011Time 10.59INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zg30TD 65536SOLVENT CDCl3NS 2DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 71.8DW 60.800 usecDE 6.50 usecTE 294.2 KD1 1.00000000 secTD0 1



NAME XS-1-6-A1EXPNO 4PROCNO 1Date_ 20111012Time 11.03INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zgpg30TD 65536SOLVENT CDCl3NS 301DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 294.6 KD1 2.00000000 secD11 0.03000000 secTD0 1



210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

14.069

17.837

19.201

21.125

21.571

29.390

30.794

32.493

34.045

34.517

35.176

36.017

44.282

45.021

46.275

46.608

48.679

50.679

67.991

71.801

76.843

77.161

77.479

170.599

211.238

213.155


42


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.8656

0.8844

1.1055

1.1229

1.1386

1.1658

1.4158

1.4230

1.4481

1.4562

1.5164

1.5236

1.5382

1.5510

1.5583

1.5858

1.5917

1.6179

1.6576

1.6920

1.7404

1.7739

1.8628

2.0375

2.0547

2.0659

2.0844

2.0955

2.1861

2.1996

2.2211

2.2276

2.2350

2.2409

2.2598

2.2653

2.2724

2.2784

2.3005

2.3171

2.3299

2.3483

2.6288

2.6456

2.6652

2.6819

2.7014

2.7180

3.3211

3.3262

3.3439

3.3484

3.3554

3.3608

3.3656

3.3731

3.3949

3.4132

3.4357

5.2396

5.2515

5.2674

5.2792

5.2950

5.3068

7.2602

3.073

6.017

2.922

5.140

2.916

1.070

3.091

1.005

4.034

1.000







210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

11.482

15.290

15.389

19.680

21.234

23.908

29.531

30.933

35.251

35.347

45.750

47.040

54.702

54.920

68.758

76.842

77.161

77.478

101.824

170.710

212.790


43


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

2.5746

0.4361

0.9223

0.9352

0.9404

1.0303

1.0478

1.0654

1.0937

1.1113

1.1290

1.4745

1.4983

1.5067

1.5499

1.5575

1.5822

1.5914

1.6014

1.6115

1.6267

1.6346

1.7067

1.7425

1.9348

1.9479

1.9631

1.9779

1.9924

2.0060

2.1720

2.1832

2.2012

2.2122

2.5442

2.5575

3.1705

3.1930

3.2106

3.3497

3.3677

3.3852

3.3999

3.4176

3.4346

3.5796

5.8848

5.8915

5.8972

5.9043

7.1600

5.896

2.823

3.066

1.135

3.219

0.987

1.062

1.121

1.029

1.092

3.266

1.018

1.000

NAME XS-1-31-A1EXPNO 11PROCNO 1Date_ 20111101Time 16.36INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT C6D6NS 4DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 128DW 60.800 usecDE 6.50 usecTE 302.5 KD1 1.00000000 secTD0 1



NAME XS-1-31-A1EXPNO 14PROCNO 1Date_ 20111103Time 21.01INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT C6D6NS 6000DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 228DW 20.800 usecDE 6.50 usecTE 300.2 KD1 2.00000000 secD11 0.03000000 secTD0 1



210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

11.515

15.522

15.566

20.798

25.664

34.679

39.898

40.979

42.991

48.151

54.951

55.051

64.394

102.879

117.846

127.820

128.062

128.303

134.708


44


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.9618

0.9800

1.0336

1.4933

1.5019

1.5145

1.5298

1.5358

1.5455

1.5497

1.5596

1.5691

1.5858

1.6090

1.6116

1.6191

1.6338

1.6445

1.6517

1.8089

1.8231

1.8480

1.8588

1.8872

1.8943

2.0856

2.0926

2.1076

2.1147

2.1286

2.1356

2.1506

2.1577

2.2591

2.2705

2.2950

2.3077

2.3116

2.3193

2.3236

2.6228

2.6370

2.6510

2.6657

2.6799

2.6940

3.7026

3.7177

3.7246

3.7303

3.7397

3.7454

3.7524

3.7675

3.8845

3.8934

3.8965

3.9063

3.9178

3.9339

3.9452

3.9556

3.9579

3.9673

4.4042

4.4327

4.6208

4.6493

6.1554

6.1625

6.1685

6.1756

7.2603

7.2699

7.2761

7.2852

7.2928

7.3024

7.3068

7.3136

7.3169

7.3302

7.3443

7.3470

7.3511

7.3615

7.3652

3.035

3.023

2.111

1.058

1.019

1.038

2.052

1.011

1.054

4.084

1.007

1.009

1.000

5.163

NAME XS-33-A1EXPNO 1PROCNO 1Date_ 20101004Time 17.02INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zg30TD 65536SOLVENT CDCl3NS 8DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 90.5DW 60.800 usecDE 6.50 usecTE 294.3 KD1 1.00000000 secTD0 1



NAME XS-33-A1EXPNO 2PROCNO 1Date_ 20101004Time 17.08INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zgpg30TD 65536SOLVENT CDCl3NS 200DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 294.6 KD1 2.00000000 secD11 0.03000000 secTD0 1



210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

12.006

20.717

27.615

36.147

37.401

40.199

42.337

47.579

64.232

64.483

71.024

71.358

76.841

77.159

77.476

111.574

117.249

127.767

127.863

128.490

134.053

138.536


45


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

1.0062

1.0249

1.2716

1.4436

1.4526

1.4878

1.5145

1.5218

1.8876

1.9006

1.9240

1.9343

1.9604

1.9681

2.0163

2.0277

2.0445

2.0565

2.1539

2.1612

2.1750

2.1824

2.2012

2.2085

2.2224

2.2298

2.2921

2.2987

2.3089

2.3245

2.3317

2.3439

2.3609

2.3755

2.3794

2.3926

2.4056

2.4099

2.4241

2.8127

2.8268

2.8401

2.8600

2.8740

2.8874

3.6783

3.7252

3.7409

3.7463

3.7540

3.7618

3.7695

3.7748

3.7906

3.8713

3.8842

3.8928

3.9057

3.9286

3.9419

3.9554

3.9613

4.4346

4.4630

4.6568

4.6852

6.5835

6.5913

6.5950

6.6028

7.2604

7.2726

7.2847

7.2951

7.3061

7.3165

7.3380

7.3486

3.046

3.136

2.107

1.059

1.200

1.066

1.021

1.030

1.046

3.013

1.105

4.107

1.024

1.028

1.000

5.039







210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

12.182

21.198

27.050

33.085

33.885

36.092

38.053

47.557

51.384

64.166

64.386

71.041

71.406

76.843

77.160

77.478

111.367

127.745

127.861

128.495

135.193

138.669

140.624

167.277


46


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

1.1064

1.2222

1.4945

1.5024

1.5074

1.5159

1.5281

1.5362

1.5413

1.5496

1.6065

1.6313

1.6556

1.6645

1.6878

1.6970

1.7049

1.7168

1.7248

1.7290

1.8771

1.8897

1.9103

1.9230

1.9434

1.9559

2.0486

2.0603

2.0777

2.0892

2.1004

2.1065

2.1129

2.1160

2.1222

2.1282

2.3298

2.3343

2.3481

2.3529

2.3600

2.3659

2.3716

2.3787

2.3836

2.3973

2.7368

2.7489

2.7521

2.7642

2.7805

2.7925

2.7958

2.8079

3.7449

3.7608

3.7666

3.7738

3.7825

3.7897

3.7955

3.8114

3.8808

3.8922

3.9011

3.9038

3.9061

3.9130

3.9171

3.9341

3.9460

3.9481

3.9535

3.9608

3.9673

4.0558

4.0982

4.1291

4.4149

4.4433

4.6605

4.6890

5.5210

5.5284

5.5317

5.5389

7.2604

7.2683

7.2790

7.2900

7.3001

7.3100

7.3164

7.3194

7.3247

7.3381

7.3491

3.004

3.067

1.105

1.121

2.010

1.028

2.053

1.004

1.001

1.029

4.067

2.058

1.001

1.004

1.000

5.075

NAME XS-1-35-A1EXPNO 3PROCNO 1Date_ 20101008Time 20.31INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zg30TD 65536SOLVENT CDCl3NS 11DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 203DW 60.800 usecDE 6.50 usecTE 294.5 KD1 1.00000000 secTD0 1



NAME XS-1-35-A1EXPNO 4PROCNO 1Date_ 20101008Time 20.44INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zgpg30TD 65536SOLVENT CDCl3NS 500DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 294.7 KD1 2.00000000 secD11 0.03000000 secTD0 1



210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

12.143

21.927

26.982

33.250

33.462

36.145

37.983

47.187

62.719

64.183

64.362

70.747

72.165

76.842

77.160

77.477

111.487

119.909

127.640

127.864

128.447

138.873

146.326


47


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.9960

1.0147

1.1020

1.4986

1.5030

1.5325

1.5368

1.6158

1.6476

1.6561

1.6810

1.6863

1.7052

1.7134

1.8781

1.8912

1.9111

1.9243

1.9440

1.9569

2.0467

2.0582

2.0757

2.0870

2.1000

2.1219

2.3312

2.3453

2.3493

2.3628

2.3758

2.3799

2.3944

2.7365

2.7494

2.7633

2.7801

2.7931

2.8070

3.3634

3.7481

3.7644

3.7695

3.7769

3.7856

3.7930

3.7981

3.8143

3.8799

3.8913

3.9017

3.9127

3.9317

3.9454

3.9582

4.0131

4.0439

4.4098

4.4383

4.6119

4.6556

4.6841

5.5519

7.2605

7.2757

7.2866

7.2968

7.3353

7.3462

3.128

3.188

1.055

2.041

1.095

2.175

1.071

1.044

3.081

1.087

5.181

1.109

1.054

2.127

1.060

1.000

5.252

NAME XS-36-A1EXPNO 1PROCNO 1Date_ 20101004Time 17.20INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zg30TD 65536SOLVENT CDCl3NS 14DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 90.5DW 60.800 usecDE 6.50 usecTE 294.4 KD1 1.00000000 secTD0 1



NAME XS-36-A1EXPNO 2PROCNO 1Date_ 20101004Time 17.28INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zgpg30TD 65536SOLVENT CDCl3NS 500DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 294.9 KD1 2.00000000 secD11 0.03000000 secTD0 1



210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

12.145

21.692

27.003

33.358

33.468

36.127

37.947

47.145

55.495

64.177

64.346

67.203

70.712

72.111

76.843

77.160

77.477

95.648

111.513

122.090

127.620

127.867

128.431

138.890

142.702


48


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

0.6673

1.1074

1.1263

1.3382

1.3464

1.3566

1.3641

1.3721

1.3822

1.3902

1.4634

1.4716

1.4826

1.4947

1.5064

1.5144

1.5228

1.5512

1.5687

1.5800

1.6051

1.6151

1.6378

1.6483

1.8486

1.8576

1.8802

1.8905

1.9149

1.9264

2.0281

2.0401

2.0560

2.0680

2.6117

2.6259

2.6304

2.6382

2.6437

2.6493

2.6570

2.6614

2.7455

2.7570

2.7685

2.7749

2.7864

2.7979

3.0909

3.3398

3.3466

3.3611

3.3719

3.3887

3.3997

3.4186

3.4281

3.4343

3.4485

3.4524

3.4606

3.4646

3.4719

3.4739

3.4787

3.4870

3.4909

3.5024

3.5180

3.5302

3.5484

3.5550

3.5731

3.6806

3.6887

3.7054

3.7135

3.7997

3.8067

3.8118

3.8189

3.8277

3.8351

3.8451

3.8540

3.8608

3.8660

3.8728

4.1414

4.1702

4.2903

4.5118

4.5403

7.0633

7.0816

7.1000

7.1463

7.1601

7.1789

7.1831

7.3008

7.3191

3.083

3.149

1.208

4.381

1.167

1.091

1.154

1.089

3.118

1.036

7.267

1.018

1.114

1.137

2.000

1.289

1.122

1.131

1.067

2.150

NAME XS-1-37-A1EXPNO 3PROCNO 1Date_ 20101027Time 17.38INSTRUM spectPROBHD 5 mm PADUL 13CPULPROG zg30TD 65536SOLVENT C6D6NS 8DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 203DW 60.800 usecDE 6.50 usecTE 295.0 KD1 1.00000000 secTD0 1

======== CHANNEL f1 ========NUC1 1HP1 14.83 usecPL1 0.00 dBPL1W 8.31434441 WSFO1 400.1324710 MHzSI 32768SF 400.1300444 MHzWDW EMSSB 0LB 0.30 HzGB 0PC 1.00


NAME XS-1-37-A1EXPNO 4PROCNO 1Date_ 20101027Time 18.08INSTRUM spectPROBHD 5 mm PADUL 13CPULPROG zgpg30TD 65536SOLVENT C6D6NS 500DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 295.5 KD1 2.00000000 secD11 0.03000000 secTD0 1


======== CHANNEL f2 ========CPDPRG2 waltz16NUC2 1HPCPD2 90.00 usecPL2 0.00 dBPL12 15.66 dBPL13 15.92 dBPL2W 8.31434441 WPL12W 0.22585411 WPL13W 0.21272963 WSFO2 400.1316005 MHzSI 32768SF 100.6127436 MHzWDW EMSSB 0LB 1.00 HzGB 0PC 1.40

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

12.551

16.649

27.140

36.218

36.392

36.723

41.597

50.770

55.183

55.999

64.075

64.247

67.784

69.796

70.525

73.084

96.648

111.393

127.590

127.819

127.996

128.059

128.300

128.540

139.625


49


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.4773

0.9017

1.0951

1.1140

1.3790

1.4071

1.4350

1.4632

1.4680

1.4767

1.4882

1.4970

1.5050

1.5181

1.5304

1.5385

1.5435

1.5517

1.6612

1.6699

1.6790

1.6926

1.7010

1.7952

1.9092

1.9240

1.9422

1.9568

1.9736

1.9881

2.0103

2.0223

2.0384

2.0504

2.5772

2.5913

2.5961

2.6037

2.6093

2.6149

2.6224

2.6273

2.6413

2.8062

2.8181

2.8302

2.8341

2.8463

2.8582

3.1655

3.3919

3.4029

3.4187

3.4315

3.4471

3.4511

3.4594

3.4611

3.4709

3.4755

3.4854

3.4906

3.4947

3.5006

3.5042

3.5156

3.5729

3.5817

4.0380

4.0667

4.3890

4.4055

4.4162

4.4333

4.4493

5.2349

5.2474

5.2636

5.2761

5.2924

5.3049

7.0581

7.0764

7.0947

7.1404

7.1631

7.1772

7.2793

7.2975

1.359

2.977

2.990

3.171

1.990

2.976

1.069

1.070

1.055

1.000

2.883

5.211

1.935

1.030

3.062

1.000

1.038

1.001

1.283

2.019







210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

12.363

16.831

20.937

27.098

36.518

36.616

36.778

38.198

50.739

54.431

55.034

64.082

64.236

64.488

69.605

70.801

73.065

96.806

111.406

127.590

127.820

127.939

128.062

128.178

128.303

128.547

139.527

169.942


50


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.6471

1.1869

1.2058

1.9874

1.2874

1.3062

1.3264

1.3350

1.3431

1.3549

1.3635

1.3718

1.3936

1.3979

1.4280

1.4318

1.5342

1.5501

1.5647

1.5721

1.5997

1.6268

1.6594

1.7448

1.7668

1.7825

1.8003

1.8156

1.8311

1.8462

1.9988

2.0165

2.0280

2.2712

2.2966

2.3018

2.3155

2.3193

2.9363

2.9489

2.9627

2.9774

2.9900

3.1203

3.4405

3.4486

3.4753

3.4810

3.4948

3.4968

3.5032

4.3213

4.3375

4.3626

4.3787

4.9165

4.9293

4.9447

4.9576

4.9731

4.9858

5.1197

5.1325

5.1484

5.1610

5.1770

5.1896

7.1601

3.029

2.988

2.292

3.353

2.813

1.173

1.125

3.037

1.201

1.031

2.833

6.288

0.942

1.027

1.000

1.020

NAME XS-1-43-A1EXPNO 2PROCNO 1Date_ 20111129Time 20.15INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zg30TD 65536SOLVENT C6D6NS 4DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 25.4DW 60.800 usecDE 6.50 usecTE 294.7 KD1 1.00000000 secTD0 1



NAME XS-1-43-A1EXPNO 3PROCNO 1Date_ 20111129Time 20.22INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zgpg30TD 65536SOLVENT C6D6NS 202DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 294.9 KD1 2.00000000 secD11 0.03000000 secTD0 1



210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

12.062

16.096

20.761

26.593

36.382

36.706

36.866

38.866

39.495

49.581

53.989

55.025

64.166

64.292

68.598

76.876

96.677

110.931

127.819

128.059

128.300

169.694


51


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.5011

0.5254

0.9463

0.9582

0.9805

0.9925

1.0181

1.0275

1.0526

1.0720

1.3151

1.3294

1.3435

1.3580

1.5264

1.5546

1.5670

1.5861

1.5930

1.6008

1.7157

1.9896

2.0236

2.0279

2.1077

2.1259

2.1476

2.1762

2.1990

2.6866

2.7030

2.7216

2.7400

2.7558

2.9911

3.0037

3.0193

3.0326

3.0464

3.1138

3.3095

3.3174

3.3363

3.3458

3.3572

3.3734

3.3839

4.2929

4.3091

4.3343

4.3504

4.7653

4.7781

4.7933

4.8061

4.8214

4.8341

5.0340

5.0464

5.0627

5.0751

5.0914

5.1039

7.1600

3.040

2.097

3.208

1.086

2.139

3.169

1.142

3.141

1.049

1.007

1.155

3.017

2.029

0.993

0.953

1.020

1.000







210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

13.442

15.501

20.660

33.795

36.538

37.964

38.616

39.319

43.700

50.754

53.313

55.110

64.096

68.065

74.966

96.720

127.818

128.060

128.301

169.471

210.868


52


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.5044

0.5686

1.2020

1.2216

1.3529

1.3629

1.3734

1.3807

1.3912

1.4012

1.4630

1.4803

1.5159

1.5439

1.6920

1.7161

1.7300

1.7452

1.7591

2.2022

2.7436

2.7628

2.7772

2.7820

2.7964

2.8157

2.9716

2.9844

2.9980

2.9999

3.0137

3.0264

3.0943

3.4013

3.4117

4.2774

4.2937

4.3189

4.3351

4.8051

4.8176

4.8330

4.8458

4.8611

4.8738

4.9374

4.9505

4.9658

4.9788

4.9942

5.0072

5.8503

5.8762

6.7548

6.7807

7.1600

2.849

2.911

1.130

1.294

2.946

1.120

3.208

0.953

1.052

3.153

2.019

1.079

1.039

0.986

1.074

1.014

1.000

NAME XS-1-46-A1EXPNO 5PROCNO 1Date_ 20111205Time 15.39INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zg30TD 65536SOLVENT C6D6NS 4DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 71.8DW 60.800 usecDE 6.50 usecTE 295.1 KD1 1.00000000 secTD0 1



NAME XS-1-46-A1EXPNO 6PROCNO 1Date_ 20111205Time 15.48INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zgpg30TD 65536SOLVENT C6D6NS 312DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 203DW 20.800 usecDE 6.50 usecTE 295.3 KD1 2.00000000 secD11 0.03000000 secTD0 1



210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

13.834

17.638

20.586

38.470

39.115

39.193

39.755

48.920

49.752

55.198

63.934

67.794

74.148

96.598

126.645

127.819

128.059

128.300

154.484

169.489

199.814


53


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm0.8796

1.3803

2.0446

2.0570

2.0674

2.0798

2.3630

2.3869

3.1601

3.4449

3.4580

3.4705

3.4831

3.5561

3.5697

3.5811

3.5947

4.0640

4.4275

4.9233

4.9272

4.9535

4.9589

4.9693

4.9794

5.5312

5.5561

5.5732

5.5813

5.5978

5.6232

6.0283

6.0522

6.3120

6.3166

6.3360

6.3406

7.1600

3.129

3.099

1.019

1.000

3.034

1.949

0.970

1.001

2.011

2.023

0.992

0.978

1.000

NAME XS-1-91-A1EXPNO 1PROCNO 1Date_ 20110409Time 10.48INSTRUM spectPROBHD 5 mm PADUL 13CPULPROG zg30TD 65536SOLVENT C6D6NS 8DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 80.6DW 60.800 usecDE 6.50 usecTE 294.1 KD1 1.00000000 secTD0 1






210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

128.343

18.448

18.667

46.092

54.856

55.358

60.891

64.256

67.799

81.943

96.933

120.163

127.817

128.058

128.299

134.074

158.441

200.783


54


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm0.5856

0.9387

1.4484

1.9159

1.9219

1.9260

1.9320

3.0430

3.0923

3.0973

3.1158

3.1208

3.2981

3.3040

3.3234

3.3293

3.7788

3.7891

3.8041

3.8144

4.2062

4.9910

4.9957

5.0062

5.0097

5.0165

5.0213

5.0484

5.0521

5.6247

5.6496

5.6670

5.6745

5.6917

5.6988

5.7161

6.0051

6.0105

6.0292

6.0346

7.1598

3.156

3.148

1.011

3.060

1.040

1.061

1.053

1.921

2.123

2.004

1.000

NAME XS-1-51-A1EXPNO 1PROCNO 1Date_ 20101203Time 18.57INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT C6D6NS 8DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 71.8DW 60.800 usecDE 6.50 usecTE 297.5 KD1 1.00000000 secTD0 1



PC 1.40GB 0LB 1.00 HzSSB 0WDW EMSF 100.6278192 MHzSI 32768SFO2 400.1916008 MHzPL13W 0.14806664 WPL12W 0.32844096 WPL2W 13.56617069 WPL13 18.62 dBPL12 15.16 dBPL2 −1.00 dBPCPD2 90.00 usecNUC2 1HCPDPRG2 waltz16======== CHANNEL f2 ========

SFO1 100.6379183 MHzPL1W 55.33689499 WPL1 −2.00 dBP1 9.90 usecNUC1 13C======== CHANNEL f1 ========

TD0 1D11 0.03000000 secD1 2.00000000 secTE 298.0 KDE 6.50 usecDW 20.800 usecRG 203AQ 1.3631988 secFIDRES 0.366798 HzSWH 24038.461 HzDS 4NS 203SOLVENT C6D6TD 65536PULPROG zgpg30PROBHD 5 mm PABBO BB−INSTRUM spectTime 19.02Date_ 20101203PROCNO 1EXPNO 2NAME XS−1−51−A1

210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

13.792

17.854

44.008

54.970

55.283

64.516

65.247

69.469

96.508

121.427

127.063

127.821

128.062

128.303

132.704

157.850

192.449

210.667


55


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm1.0377

1.2866

1.4007

1.4187

1.9992

2.0053

2.0106

2.0168

2.8056

2.8298

3.0782

3.3214

3.3276

3.3465

3.3527

3.6378

3.6469

3.6529

3.6620

3.7255

3.7371

3.7506

3.7622

4.2461

5.0405

5.0463

5.0659

5.0718

5.1013

5.1068

5.1440

5.1495

5.4489

5.4727

5.5623

5.5715

5.5862

5.5954

6.1258

6.1507

6.1685

6.1754

6.1934

6.2182

7.1600

3.141

3.164

1.001

1.015

1.020

3.047

1.052

1.019

1.041

2.058

1.022

1.053

1.020

1.014

1.000







220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

16.458

18.374

42.721

55.184

56.243

57.096

58.935

65.680

70.627

96.493

118.551

127.816

128.057

128.298

135.898

140.824

219.712


56


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

-0.0392

-0.0114

0.2949

0.4398

0.9439

1.1154

1.3393

2.0870

2.0931

2.0987

2.1048

2.8356

2.8605

3.1067

3.4016

3.4076

3.4267

3.4327

3.7657

3.7778

3.7908

3.8029

3.8311

4.2803

5.1180

5.1383

5.1442

5.1597

5.1654

5.5121

6.3500

6.3754

6.3916

6.4013

6.4170

6.4427

7.1601

2.898

2.819

9.184

3.153

3.106

1.005

1.063

2.983

1.043

1.025

0.904

2.077

0.940

1.020

2.017

1.000







220 200 180 160 140 120 100 80 60 40 20 0 ppm

-5.004

-4.353

1.414

17.343

18.227

18.480

25.921

42.872

55.199

57.178

59.290

65.748

70.801

96.559

117.057

127.818

128.059

128.300

136.891

140.493

219.833


57


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.0295

0.0615

0.2956

0.4385

0.9934

1.1373

1.2929

2.2807

2.3057

2.5859

2.5980

2.6024

2.6145

3.1764

3.4082

3.4200

3.4332

3.4450

3.5543

3.5713

3.5793

3.5963

3.7038

4.4471

5.0627

5.0691

5.1081

5.1124

5.1164

5.1235

5.1424

5.1492

5.1540

5.1576

5.5827

6.3185

6.3438

6.3610

6.3690

6.3863

6.4116

7.1601

3.078

3.037

9.262

3.113

3.034

0.955

0.908

2.984

0.943

1.006

0.969

1.978

4.079

2.039

1.000







210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

-4.875

-4.074

18.294

19.483

21.404

26.025

44.544

51.111

54.756

55.152

58.281

70.097

75.729

96.811

110.004

116.190

127.820

128.060

128.302

138.195

139.466

159.576


58


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.0198

0.0531

0.2984

0.4155

0.9857

1.0324

1.2313

2.2008

2.2258

2.3220

2.3370

2.3516

3.2793

3.2914

3.3056

3.3193

3.3320

3.4521

3.4666

3.4805

3.4944

3.5104

3.6607

3.6684

5.0090

5.0122

5.0306

5.0344

5.0744

5.0801

5.0945

5.1010

5.1199

5.1263

5.5026

5.5054

5.5266

5.5294

5.5349

5.5429

5.5588

5.5667

6.2844

6.3096

6.3270

6.3348

6.3521

6.3774

7.1600

3.197

3.020

9.177

3.069

3.081

1.057

0.973

1.056

1.044

0.950

4.199

2.111

1.000

NAME XS-1-127-A1(H1)EXPNO 1PROCNO 1Date_ 20120110Time 19.44INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zg30TD 65536SOLVENT C6D6NS 6DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 203DW 60.800 usecDE 6.50 usecTE 295.4 KD1 1.00000000 secTD0 1






210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

-4.895

-4.080

18.282

19.135

21.257

26.007

44.453

51.209

56.862

58.255

63.915

75.778

109.833

116.228

127.626

127.819

128.060

128.301

138.040

139.452

159.478


59


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

-0.0248

0.0146

0.4977

0.9279

0.9447

0.9535

1.8100

1.8198

1.8287

1.8385

2.2690

2.2802

2.3213

2.3325

2.4013

2.4264

2.4460

2.4601

2.4669

2.4809

3.4381

3.4480

3.4591

3.4678

3.4770

3.4881

3.4980

3.5225

3.5309

3.6507

3.6649

3.6695

3.6830

3.6941

3.6984

3.7126

5.0027

5.0087

5.0507

5.0562

5.0759

5.0820

5.4272

5.4514

5.4698

5.4784

5.4934

5.5021

6.1559

6.1811

6.1984

6.2063

6.2236

6.2488

7.1600

2.970

2.917

3.135

3.011

9.167

1.000

1.036

0.998

1.038

0.978

1.084

0.995

1.168

2.211

2.107

1.018

NAME XS-1-130-A1EXPNO 1PROCNO 1Date_ 20110629Time 22.41INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zg30TD 65536SOLVENT C6D6NS 16DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 90.5DW 60.800 usecDE 6.50 usecTE 297.7 KD1 1.00000000 secTD0 1






210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

-4.972

-4.029

16.085

18.237

19.093

25.948

44.151

48.518

48.674

53.258

58.101

61.455

69.170

72.844

116.765

126.692

127.819

128.060

128.301

137.318

139.594


60


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.0597

0.0655

0.4547

0.8859

0.9950

1.0680

1.1415

1.6028

1.6135

1.6254

1.6361

1.8717

1.8849

1.8981

2.1228

2.4692

2.4944

3.4975

3.5091

3.5236

3.5363

3.5481

3.5812

3.5944

3.6039

3.6074

3.6171

3.6304

3.6436

3.7888

3.7976

5.0376

5.0439

5.0704

5.0774

5.0859

5.0962

5.1028

5.4373

5.4402

5.4612

5.4641

5.4804

5.4893

5.5040

5.5129

6.2233

6.2488

6.2654

6.2743

6.2910

6.3166

7.1602

2.954

2.947

3.135

9.339

3.065

3.154

1.036

0.971

1.000

1.009

1.045

1.045

1.019

2.071

2.044

1.000







210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

-4.877

-3.965

16.139

18.310

19.267

26.052

27.476

43.760

53.586

57.590

59.309

61.835

70.467

81.759

115.913

126.062

127.822

128.063

128.304

138.501

140.630


61


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.0655

0.4661

0.9998

1.0655

1.1347

1.2300

1.5521

1.6173

1.6256

2.2232

2.7384

2.7636

2.9520

2.9725

3.7941

3.7985

4.2286

4.2328

4.2373

4.2427

4.2508

4.2621

4.2670

4.9835

4.9874

4.9912

5.0096

5.0134

5.0172

5.1088

5.1154

5.1294

5.1345

5.1407

5.1513

5.1552

5.1591

5.1717

5.1782

5.1943

5.1983

5.2021

5.4959

6.0517

6.0658

6.0777

6.0923

6.1090

6.1208

6.1350

6.2663

6.2916

6.3089

6.3169

6.3342

6.3595

7.1599

6.156

9.192

3.052

3.031

3.212

1.050

0.907

1.016

0.968

1.027

1.095

1.165

3.091

2.093

1.000

1.068







210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

-4.991

-4.061

15.905

18.240

18.961

25.969

26.380

44.497

53.798

58.398

69.836

70.051

82.759

116.589

126.873

127.818

128.058

128.299

137.195

138.662

201.083


62


9 8 7 6 5 4 3 2 1 0 ppm

0.0532

0.0655

0.4661

0.9124

0.9629

0.9786

0.9998

1.0098

1.0307

1.0655

1.1347

1.2300

1.5521

1.6173

1.6256

2.1146

2.2232

2.7384

2.7636

2.9520

2.9725

3.7941

3.7985

4.2373

4.2427

4.2508

4.2621

4.9835

4.9874

4.9912

5.0096

5.0134

5.0172

5.1088

5.1154

5.1294

5.1345

5.1407

5.1513

5.1552

5.1591

5.1717

5.1782

5.1943

5.1983

5.2021

5.4959

6.0517

6.0658

6.0777

6.0923

6.1090

6.1208

6.1350

6.2663

6.2916

6.3089

6.3169

6.3342

6.3595

7.1599

6.156

9.192

3.052

3.031

3.212

1.050

1.015

1.016

0.968

1.027

1.095

1.165

3.091

2.093

1.000

1.068







210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

-4.862

-3.958

16.280

18.314

20.245

25.976

26.048

27.195

30.086

44.908

53.898

58.110

62.273

70.438

74.185

84.348

113.931

116.097

125.947

127.819

128.060

128.301

138.741

141.497

143.196


63


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm3.6506

0.0447

0.0533

0.4306

0.8724

0.9704

1.2634

1.3026

1.5858

1.6023

1.7147

1.7261

1.7589

1.7702

2.2609

2.3050

2.6060

2.6312

3.6397

3.6476

3.6585

3.7739

3.7836

3.8864

3.8939

3.9028

3.9103

5.0601

5.0660

5.0852

5.0911

5.2017

5.2071

5.2442

5.2498

5.3846

5.4084

5.5092

5.5191

5.5329

5.5429

6.1790

6.2041

6.2217

6.2294

6.2468

6.2719

7.1600

2.913

2.944

3.059

9.024

3.060

3.031

1.053

1.047

1.026

1.024

1.087

1.030

1.000

1.132

1.079

1.033

1.076

1.089




NAME XS-1-134-A1EXPNO 14PROCNO 1Date_ 20111001Time 2.58INSTRUM spectPROBHD 5 mm PABBO BB-PULPROG zgpg30TD 65536SOLVENT C6D6NS 5000DS 4SWH 24038.461 HzFIDRES 0.366798 HzAQ 1.3631988 secRG 71.8DW 20.800 usecDE 6.50 usecTE 300.1 KD1 2.00000000 secD11 0.03000000 secTD0 1



210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

-4.932

-3.977

16.159

18.287

19.894

20.644

25.976

34.514

44.980

51.874

57.781

62.778

70.094

78.096

85.285

94.711

116.858

126.859

127.819

128.060

128.301

137.140

139.659

173.868


64


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.0246

0.0512

0.4346

0.9536

0.9740

1.3045

1.3596

1.7018

1.7189

1.9606

1.9788

2.6976

2.7229

3.7984

3.8080

4.0492

4.0577

4.0664

4.0748

4.1361

4.1442

5.0435

5.0494

5.0687

5.0745

5.1622

5.1675

5.2049

5.2101

5.4086

5.4324

5.5244

5.5342

5.5481

5.5579

5.9308

5.9487

5.9669

5.9850

6.1826

6.2078

6.2253

6.2330

6.2505

6.2757

7.1600

3.013

3.035

9.006

3.077

3.062

3.036

1.062

3.029

1.049

1.104

1.071

1.049

1.086

1.055

1.078

1.086

1.000

1.043







210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

-4.927

-3.985

14.138

16.246

18.277

20.085

21.094

25.976

45.163

52.007

57.837

62.912

70.136

81.257

83.552

95.333

116.798

126.777

127.164

127.818

128.059

128.300

137.166

139.783

142.688

167.844


65


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.0167

0.0450

0.4222

0.9495

0.9632

1.2635

1.3841

1.3999

1.4178

1.7400

1.7577

2.6292

2.6546

6.6946

6.6969

6.7483

6.7506

3.7837

3.7934

4.0708

4.0800

4.0886

4.0978

4.3867

4.3942

5.0347

5.0407

5.0598

5.0658

5.1332

5.1388

5.1759

5.1814

5.4143

5.4379

5.5225

5.5324

5.5462

5.5561

6.1737

6.1989

6.2164

6.2241

6.2416

6.2668

6.7127

6.7149

6.7305

6.7327

7.1607

3.053

2.977

9.262

3.135

3.208

3.089

3.207

1.105

1.090

1.075

1.156

1.084

1.104

1.131

1.107

1.107

1.148

1.000







210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

-4.947

-4.008

15.388

16.288

18.270

20.180

21.228

25.971

45.183

51.990

57.901

62.749

70.084

76.687

84.016

95.794

116.828

126.765

127.819

128.060

128.302

128.713

137.085

139.738

139.779

168.663


66


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

3.5473

3.5754

0.4242

0.8396

1.1428

1.1635

1.2561

1.2827

1.6350

1.6517

1.9706

1.9888

2.6526

2.6763

3.5574

3.5663

3.9881

3.9965

4.0051

4.0135

4.0686

4.0768

4.9409

4.9461

4.9667

4.9718

5.0932

5.0969

5.1361

5.1397

5.3356

5.3592

5.5717

5.5817

5.5954

5.6055

5.8216

5.8467

5.8647

5.8709

5.8891

5.9145

5.9338

5.9518

5.9697

7.1600

3.032

1.003

3.083

3.145

1.082

3.054

0.986

1.157

1.027

0.982

1.049

1.073

1.048

1.000

2.156







210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

14.128

15.431

19.977

20.847

45.005

51.958

56.301

62.744

69.900

81.145

83.529

95.298

119.127

127.143

127.374

127.819

128.060

128.301

135.619

139.737

142.675

167.824


67


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm1.0358

1.1394

1.4163

1.5709

2.2458

2.2640

2.5232

2.5399

2.8141

2.8181

2.8378

2.8418

4.8388

4.8466

4.8646

4.8728

4.8813

4.8894

5.1532

5.1577

5.1783

5.1827

5.2200

5.4900

5.5145

5.5324

5.5391

5.5568

5.5815

5.8781

5.9021

6.6583

6.6697

6.6753

6.6940

6.7127

7.2599

3.005

3.106

3.143

3.015

0.991

0.973

0.973

1.026

2.101

1.033

1.000

2.084

NAME XS-1-144-A1EXPNO 11PROCNO 1Date_ 20120504Time 19.26INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zg30TD 65536SOLVENT CDCl3NS 32DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 203DW 60.800 usecDE 6.50 usecTE 294.2 KD1 1.00000000 secTD0 1






210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

12.880

14.601

19.682

22.434

47.019

60.825

62.790

63.979

76.843

77.160

77.478

82.337

83.134

94.169

121.775

126.097

127.014

132.387

144.823

157.112

168.380

201.556


68


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm

0.4318

0.8321

1.1351

1.1559

1.2314

1.3111

1.3799

1.3978

1.6653

1.6829

2.5945

2.6179

3.5241

3.5335

3.5430

3.5520

4.0022

4.0113

4.0198

4.0289

4.3123

4.3201

4.9357

4.9406

4.9614

4.9662

5.0695

5.0732

5.1126

5.1161

5.3382

5.3618

5.5684

5.5785

5.5921

5.6021

5.8154

5.8401

5.8585

5.8647

5.8830

5.9078

6.6974

6.7152

6.7333

6.7495

7.1600

3.123

1.101

3.179

3.037

3.181

1.006

0.948

0.982

0.966

0.929

1.050

1.054

1.017

1.045

0.989

1.000

NAME XS-1-136-A1EXPNO 1PROCNO 1Date_ 20111217Time 14.58INSTRUM spectPROBHD 5 mm PABBI 1H/PULPROG zg30TD 65536SOLVENT C6D6NS 32DS 2SWH 8223.685 HzFIDRES 0.125483 HzAQ 3.9846387 secRG 203DW 60.800 usecDE 6.50 usecTE 294.9 KD1 1.00000000 secTD0 1






210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm

15.397

15.478

20.072

20.973

45.019

51.943

56.366

62.573

69.842

76.578

84.003

95.778

119.114

127.331

127.818

128.059

128.300

128.680

135.563

139.748

168.641


69


7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 ppm1.0083

1.1590

2.7473

2.7518

2.7709

2.7755

1.4225

1.5567

2.0285

2.0464

2.5487

2.5662

4.8865

4.8953

4.9039

4.9128

5.0860

5.0941

5.1490

5.1737

5.1957

5.4851

5.5095

5.5274

5.5342

5.5518

5.5767

5.8807

5.9046

6.6713

6.6761

6.6951

6.7001

6.9778

6.9962

7.0145

7.0327

7.2600

3.045

3.062

3.025

3.019

1.039

1.041

1.062

0.966

2.058

1.106

1.018

1.123

1.000







210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

12.842

16.179

19.782

22.498

47.026

60.620

62.794

64.033

76.842

77.160

77.477

77.765

83.802

94.507

121.734

126.970

127.684

132.374

141.886

157.123

169.529

201.605


70


total synthesis of (±)-pallambins c and d · supplementary information for total synthesis of...

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