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doi.org/10.26434/chemrxiv.8977673.v1

Engaging Aldehydes in CuH-Catalyzed Reductive Coupling Reactions:Stereoselective Allylation from 1,3-Diene PronucleophilesChengxi Li, Kwangmin Shin, Richard Liu, Stephen L. Buchwald

Submitted date: 22/07/2019 • Posted date: 23/07/2019Licence: CC BY-NC-ND 4.0Citation information: Li, Chengxi; Shin, Kwangmin; Liu, Richard; Buchwald, Stephen L. (2019): EngagingAldehydes in CuH-Catalyzed Reductive Coupling Reactions: Stereoselective Allylation from 1,3-DienePronucleophiles. ChemRxiv. Preprint.

Recently, CuH-catalyzed reductive coupling processes involving carbonyl compounds and imines hasbecome an attractive alternative to traditional methods for stereoselective addition to carbonyls due to theability to use readily accessible and stable olefin-derived pronucleophiles as surrogates for organometallicreagents. However, the inability to use aldehydes, which traditionally reduce too rapidly in the presence ofcopper hydride complexes to be viable substrates, has been a major limitation. We show that by exploitingrelative concentration effects through slow addition, we can invert this intrinsic reactivity and achieve thereductive coupling of 1,3-dienes with aldehydes. Using this method, both aromatic and aliphatic aldehydescan be transformed to valuable products with high levels of diastereo- and enantioselectivity and in thepresence of many useful functional groups. Furthermore, using a combination of theoretical (DFT) andexperimental methods, important mechanistic features of this reaction related to stereo- and chemoselectivitywere uncovered.

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http://doi.org/10.26434/chemrxiv.8977673.v1

https://chemrxiv.org/authors/Kwangmin_Shin/7022258

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https://chemrxiv.org/articles/Engaging_Aldehydes_in_CuH-Catalyzed_Reductive_Coupling_Reactions_Stereoselective_Allylation_from_1_3-Diene_Pronucleophiles/8977673/1?file=16437863







Engaging Aldehydes in CuH-Catalyzed Reductive Coupling Reac-

tions: Stereoselective Allylation from 1,3-Diene Pronucleophiles

Chengxi Li,† Kwangmin Shin,† Richard Y. Liu, and Stephen L. Buchwald*

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States

ABSTRACT: Recently, CuH-catalyzed reductive coupling processes involving carbonyl compounds and imines has become an at-

tractive alternative to traditional methods for stereoselective addition to carbonyls due to the ability to use readily accessible and

stable olefin-derived pronucleophiles as surrogates for organometallic reagents. However, the inability to use aldehydes, which tra-

ditionally reduce too rapidly in the presence of copper hydride complexes to be viable substrates, has been a major limitation. We

show that by exploiting relative concentration effects through slow addition, we can invert this intrinsic reactivity and achieve the

reductive coupling of 1,3-dienes with aldehydes. Using this method, both aromatic and aliphatic aldehydes can be transformed to

valuable products with high levels of diastereo- and enantioselectivity and in the presence of many useful functional groups. Further-

more, using a combination of theoretical (DFT) and experimental methods, important mechanistic features of this reaction related to

stereo- and chemoselectivity were uncovered.

■ INTRODUCTION

The addition of nucleophilic organometallic reagents, such

as those based on Mg (Grignard), B, Si, Sn and Zn, to carbonyl

derivatives is a key reaction for C–C bond formation.1 Accord-

ingly, the development of methods to accomplish this transfor-

mation in a catalytic, stereoselective manner have been the sub-

ject of widespread research efforts.2 Recently, breakthroughs in

transition metal catalysis have enabled the use of olefin-derived

nucleophiles, one of the most convenient and readily available

classes of compounds, as surrogates of traditional organometal-

lic reagents in carbonyl addition processes.3-10 Following pio-

neering work by Krische using Rh4a,b, Ru5, Ir6, and Ni cata-

lysts,7e several research groups, including ours, have developed

a number of CuH-catalyzed processes for reductive C–C bond

formation from π-unsaturated pronucleophiles (Figure 1A).9,10

Each of these metals is associated with distinct catalytic

mechanisms and complementary reactivity, and hence, features

respective advantages and deficiencies. In the case of Cu, the

most notable advantages include mild conditions, high stereose-

lectivity, and exceptional tolerance for polar functional

groups.9,10 On the other hand, the proclivity of CuH intermedi-

ates to participate in direct reduction of carbonyl compounds

has so far limited the generality of this strategy: to date, only

the functionalization of ketones and imines using relatively ac-

tivated alkenes such as allenes, enynes, styrenes have been suc-

cessfully accomplished (Figure 1B).9,10 The conspicuous ab-

sence of aldehydes, the most common class of electrophiles in

carbonyl addition reactions, can be explained by the rate of their

direct reaction with CuH species, which is sufficiently high that

the olefinic partner typically does not have the chance to partic-

ipate in hydrocupration.11

With the aim of addressing this important limitation, we

herein report the expansion of the scope of CuH-catalyzed re-

ductive olefin–carbonyl coupling to aldehyde starting materials,

using a combination of ligand-conferred regioselectivity and ki-

netic control through metered addition. To prove our concept,

we selected 2-substituted 1,3-dienes as relatively unactivated

model pronucleophiles (Figure 1B). 2-Substituted allyl groups

are difficult to introduce using stoichiometric organometallic

reagents, and few catalytic methods have been reported for their

stereoselective installation.2,12

Figure 1. Overview of CuH-catalyzed reductive coupling of π-

unsaturated pronucleophiles with carbonyl derivatives.

Considering previous mechanistic studies,9f we envisioned

that our proposed transformation would proceed through hydro-

cupration of a diene to generate a mixture of allylcopper com-

plexes represented by II (Figure 1C). One or more of these spe-

cies could engage an aldehyde coupling partner in a stereose-

lective migratory insertion process to form the copper alkoxide

III, from which metathesis with a hydrosilane (IV) would re-

generate LCuH (I) and the desired product (V) in silyl-protected

form. Clearly, the diene hydrocupration must be faster than the

rapid direct reduction of the aldehyde, which is contrary to the

intrinsic kinetic preferences of these elementary reactions (18.5

vs. 13.9 kcal/mol calculated free energy barriers for diene and

aldehyde hydrocupration respectively, see below). In this article,

we describe the optimization of a reaction system that displays

this inverted chemoselectivity, its applications to the highly re-

gio-, diastereo- and enantioselective allylation of both aliphatic

and aromatic aldehydes, and mechanistic studies that explain

the origin of these selectivities.

■ RESULTS AND DISCUSSION

We initiated our study by examining reactions of p-

anisaldehyde (1a) and 2-phenyl-1,3-butadiene (1b) under re-

action conditions previously described for CuH-catalyzed

ketone allylation.9e,f With (S,S)-QuinoxP*(L1) as the ligand,

the desired product 1 was obtained in 48% yield, with exclu-

sive branched-selectivity and excellent preference for the in-

dicated diastereomer (11:1 dr). However, the major diastere-

omer was formed with only a moderate level of enantiose-

lectivity (68:32 er, Table 1, entry 1). No desired homoallylic

alcohol 1 was obtained when (R)-DTBM-SEGPHOS (L2)

was used as the ligand: complete reduction of the aldehyde

was observed instead (Table 1, entry 2). JosiPhos13 deriva-

tive SL-J011-1 (L3), a ligand which had been employed with

good results in ketone allylation,9f was also examined. The

corresponding test reaction provided 1 in moderate (57%)

yield, with 8:1 dr and 85:15 er (Table 1, entry 3). Further

evaluation of commercially available common chiral ligands

revealed (S,S)-Ph-BPE (L4) to be optimal (Table 1, entry 4),

providing 75% yield of 1 was obtained with excellent dr

(21:1) and er (96.5:3.5). Table 1. Evaluation of Reaction Conditions for the CuH-Catalyzed

Allylation of 4-Methoxybenzaldehyde.a

Entry Ligand Cat.

(%)

Temp.

(°C)

Yieldb

1 (%)

dr erc

(major)

1 L1 5 rt 48 11:1 68:32

2 L2 5 rt 0 -- --

3 L3 5 rt 57 8:1 85:15

4 L4 5 rt 75 21:1 96.5:3.5

5 L4 5 40 71 24:1 95.5:4.5

6 L4 1 rt 90 13:1 94:6

7 L4 1 0 94 13:1 95:5

8 d L4 1 0 33 9:1 95:5

9 e L4 1 0 97 10:1 91:9

aConditions: 1a (0.1 mmol, 1 equiv), 1b (2 equiv), Cu(OAc)2 (0.01

or 0.05 equiv), ligand (0.012 or 0.06 equiv), dimethoxy(me-

thyl)silane (4.0 equiv) in solvent (0.2 mL). 1a was added slowly by

syringe pump (1.0 mol/L, 1.0 uL/min); see the Supporting Infor-

mation for details. bYield and diastereomeric ratio were determined

by 1H NMR spectroscopy of the crude reaction mixture, using di-

bromomethane as an internal standard. cEnantiomeric ratio was de-

termined by HPLC or SFC analysis on commercial chiral columns,

and the relative configuration of 1 was determined by comparing

its NMR and optical rotation data with reported data.14 dWithout

metered addition. eWith slower addition rate (1.0 mol/L, 0.5

uL/min).

With a slight increase in reaction temperature (40 ˚C),

both the yield and er diminished slightly (Table 1, entry 5).

Furthermore, the results were very sensitive to the catalyst

loading: excellent yield (90%) was achieved without losing

high diastereo- and enantioselectivity (13:1 dr, 94:6 er) by

decreasing the catalyst loading from 5.0 to 1.0 mol% (Table

1, entry 6). Lowering the temperature to 0 ˚C proved to be

beneficial, increasing the yield to 94% (Table 1, entry 7). Me-

tered addition of the aldehyde is also important for this allyla-

tion process: by adding the aldehyde in a single batch at the start

of the reaction, only 33% of target product could be observed.

However, extremely slow addition rates will decrease the enan-

tioselectivity slightly and are not advantageous for the yield

(Table 1, entry 8 and 9).

We next explored the scope of the asymmetric reductive

coupling of aldehydes with 1,3-dienes. As depicted in Table 2,

a range of chiral homoallylic alcohols were prepared in excel-

lent yields and levels of enantiomeric purity. Simple benzalde-

hyde was successfully transformed into the corresponding

homoallylic alcohol 2 in good yield with moderate diasterose-

lectivity, but high enantioselectivity. Notably, aliphatic primary

(3, 4), secondary (5), and tertiary (6) aldehydes were also com-

patible substrates with our protocol, providing uniformly excel-

lent yield, dr and er. Using ferrocenecarboxaldehyde, we ob-

tained enantiomerically enriched ferrocene derivative 7. Fur-

thermore, substrates containing heterocycles, such as a furan (8),

a thiophene (9) and an indole (10), were all tolerated under the

reaction conditions. A thioether could also be effectively con-

verted into secondary alcohol 11 with good stereoselectivity.

Next, we assessed the scope of 1,3-diene pronucleophiles

(Table 2). The reaction proceeded efficiently with dienes bear-

ing electron-donating (7, 8) or electron-withdrawing (9, 10) aryl

substituents at 2-position. Various heterocycles are well toler-

ated on the diene component, including a thiophene and an in-

dole, reacting efficiently with both aromatic and aliphatic alde-

hyde partners (11-14) with excellent diastereo- and enantiose-

lectivity.

2-Alkyl substituted dienes could also be effectively con-

verted. For instance, 2-cyclohexyl-1,3-butadiene coupled well

with a range of vinyl (15) and aliphatic aldehydes (16-18) with

high selectivities, although the yields are moderate. In particular,

simple aliphatic aldehydes such as acetaldehyde are suitable

starting materials for this reaction (16). Even extreme steric

bulk on both components could be tolerated: using pivaldehyde

and an adamantyl-substituted diene, homoallyl alcohol 19 was

obtained with moderate yield (48%) and excellent diastereo-

and enantioselectivity (>20:1 dr, 99.5:0.5 er). Finally, a natu-

rally occurring diene, myrcene, proved to be an effective rea-

gent, providing 20 with good yield and useful stereoselectivity.

Table 2. Evaluation of the Scope of the Aldehyde Allylation with Branched Dienes.a

aYields indicate the isolated yield of product as a mixture of two diastereomers on a 1.0 mmol scale. Diastereomeric ratios were determined

by 1H NMR spectroscopy for both the crude and purified products; enantiomeric ratios were determined by HPLC, SFC or chiral GC analysis

on commercial chiral columns. Yields, diastereomeric ratios, and enantiomeric ratios are the averages for two identical runs. See Supporting

Information for full details.

■ MECHANISTIC STUDIES

By analogy to other copper-catalyzed reductive olefin–ke-

ton9b,f and olefin–imine coupling9a reactions, we proposed that

the current reaction proceeds through the mechanism illustrated

in Figure 1C. Previous computational and experimental inves-

tigations of related transformations have revealed, in intricate

detail, the sequence of events and controlling factors that dictate

the regio-, diastereo- and enantioselectivity observed in these

transformations.9f However, we were interested in several ques-

tions pertaining to the mechanism and selectivity that are par-

ticular to this aldehyde allylation. First, we wanted to confirm

the feasibility of our proposed series of elementary steps, as

well as their relative rates, their reversibility, and the identity of

the selectivity-determining step(s). It is important to note, how-

ever, that metered addition of the aldehyde, which presumably

maintains a low steady-state concentration of aldehyde, is cru-

cial to obtaining high yields of product. Thus, it is necessary

that our model to account for this effect. Second, we hoped to

explain the stereochemical outcome of our reaction. Specifi-

cally, our rationale should both identify the step(s) that control

the diastereo- and enantioselectivity (allylcopper isomerization,

C–C bond formation, -bond metathesis, or a combination

thereof), as well as the specific ligand–substrate interactions re-

sponsible for destabilizing the disfavored stereoisomeric path-

ways. Finally, we wanted to confirm experimentally that com-

peting aldehyde vs. diene insertion into a copper(I) hydride

complex determines the chemoselectivity with regard to reduc-

tion vs. the desired coupling.

Figure 2. Computed energy profiles for CuH-catalyzed allylation (blue) and reduction (red) of benzaldehyde (1c). These calculations

were performed at the M06-2X/SDD–6-311+G(d,p)/SMD(toluene)//B3LYP/SDD–6-31G(d) level of theory. Standard free energies

are relative to infinitely separated I and reactants (1c and 1b). See the Supporting Information for details.

Figure 3. Stereochemical model for the CuH-catalyzed aldehyde allylation process. DFT-optimized lowest energy transition state

structures for the C–C bond formation step, leading to the major stereoisomer (left), the minor diastereomer (middle) and the minor

enantiomer (right) of product 2. See the Supporting Information for details.

We first turned to DFT-based modeling to address the first

two questions. The computed Gibbs free energy profile, using

model diene 1b and benzaldehyde (1c) as model substrates, is

shown in Fig. 2. Starting from L*CuH (I), where L* = (S,S)-

Ph-BPE, irreversible hydrocupration of 1b takes place prefer-

entially through its s-cis conformation and with facial selectiv-

ity to generate the S enantiomer of branched allylcopper com-

plex IIa. We found that (S)-IIa can isomerize rapidly to a nearly

isoenergetic linear isomer IIb-cis, in which the Ph and Me al-

kene substituents are mutually cis. While this isomerization is

associated with an energetic barrier of 7.1 kcal/mol (TS3-cis),

there also exists a second, slower isomerization pathway (13.0

kcal/mol barrier) leading to more stable linear isomer IIb-trans

(4.0 kcal/mol more stable than IIa), in which the Ph and Me are

mutually trans.

In accordance with the Curtin–Hammett principle, the iso-

mer of II (e.g., IIa, IIb-cis, IIb-trans) through which the reac-

tion proceeds will depend on the rate of the subsequent addition

step relative to the isomerization processes. However, prior to

further elaboration on this aspect, we first need to more pre-

cisely consider the effect of slow addition of aldehyde on the

mechanistic model in general. While it is conventional to plot

energy diagrams using standard thermodynamic parameters,

(i.e., those at 1 M solution for solutes), true relative free ener-

gies depend on the concentrations of the species involved. In

cases where two reactants might have concentrations differing

by many orders of magnitude during steady-state catalyst turn-

over, it is particularly important to consider relative concentra-

tion effects in the interpretation of an energy diagram.15

Accordingly, in the reaction under consideration, we noted

that the metered addition of aldehyde over several hours should

ensure that the concentration of the aldehyde is very low rela-

tive to the other reactants. The presence of this concentration

disparity is equivalent to raising the free energy of all states

wherein aldehyde is associated with the catalyst (Figure 2, high-

lighted in grey) relative to states in which the aldehyde is free

(in white). Indeed, we find that if, by relative concentration ef-

fects, TS1 is raised in energy by more than about 4.6 kcal/mol

relative to TS2a, hydrocupration can be favored over direct re-

duction of the aldehyde, as is observed in the reaction.

A less obvious consequence is that the reaction of the cop-

per allyl species is also slowed, which has implications on re-

versibility of allylcopper isomerization. We examined eight di-

astereomeric transition states for allylcopper addition to the al-

dehyde (Figure 4, boxed and labeled TS4-cis/trans). Consider-

ing standard free energies alone, it would appear that reaction

of the cis-allyl complex IIb-cis through (S,S)-TS4-cis is suffi-

ciently facile that competing isomerization to the more stable

IIb-trans should be kinetically precluded. However, with spe-

cies highlighted in grey raised in energy by the amount (>4.6

kcal/mol) required to avoid direct aldehyde reduction, reaction

of IIb-cis with aldehyde through the TS4-cis transition states

necessarily become more challenging than reversible isomeri-

zation to IIb-trans. In this scenario, the predicted major reac-

tion pathway (highlighted in blue) proceeds through (S,R)-TS4-

trans, leading to the diastereomer of product that is experimen-

tally observed to be predominant ((S,R)-V).

We next examined the transition state structures to eluci-

date the origin of stereoselectivity in the addition step. Mono-

meric complexes of Ph-BPE-ligated copper are known adopt a

conformation whose steric profile is well approximated by a

quadrant model.16 For instance, in the preferred six-membered

cyclic transition state (Figure 3, left panel),17 the largest substit-

uents of both the allyl component and the aldehyde component

are directed into the less hindered (white) quadrants during the

C–C bond formation. In contrast, minor enantiomer of product

can form if the aldehyde attacks the opposite face of the diene

(Figure 3, center panel). However, a steric clash is created be-

tween the aryl substituent of the diene and the Ph substituent of

the ligand (bottom-right quadrant), which destabilizes this

structure. Furthermore, unfavorable steric interactions between

the aldehyde substituent and the other Ph group on the ligand

(top-left quadrant) causes the structure to distort from its ideal,

chair-shaped cyclic geometry. Finally, a minor diastereomer

can form if, relative to the favored transition state, the opposite

face of the aldehyde is attacked (Figure 3, right panel). The

dominant destabilizing interaction in this case is between the

aldehyde substituent and the Ph group of Ph-BPE in the top-left

quadrant. Overall, this model determines the correct sense of

selectivity, although the magnitude is somewhat overestimated

relative to experiment (95:5 er, 5:1 dr).

We also performed kinetic experiments to further explore

the effect of slow addition on the chemoselectivity of our reac-

tion (Figure 4). Under the standard conditions, except with no

diene present, the reduction of aldehydes is extremely rapid. In

our experiment, benzaldehyde was fully consumed within 40

min, forming the silyl-protected benzyl alcohol (Figure 4, top

panel). If a single equivalent of diene is added at the beginning

of the reaction, the corresponding reductive coupling product is

observed to form in a roughly 1:9 ratio with the reduction prod-

uct (Figure 4, middle panel). Notably, however, the overall con-

sumption of starting material has been retarded, with the reac-

tion now requiring over 3 h to reach full consumption of starting

material. Finally, when a large excess of diene is added at the

beginning of the reaction (5.0 equiv diene, Figure 4, bottom

panel), the reductive coupling product is observed to form at a

higher ratio relative to the reduction product. Simultaneously,

the total consumption of starting material is further retarded.

Two conclusions can be drawn from these data. First, the

correlation of the product-to-reduction ratio with the diene-to-

aldehyde concentration ratio supports the proposed the role of

slow addition in our mechanistic scheme. In Figure 2, higher

concentration of diene lowers the energy of the blue pathway

relative to the red pathway, and therefore leads to increased for-

mation of the coupling product. Second, the seemingly inhibi-

tory effect of the diene explains why the slow addition protocol

must be conducted over a relatively long timespan (~3.5 h), in

spite of the fact that we are trying to outcompete an extremely

rapid reaction (half-life on the order of several min). Under the

conditions of our protocol, at large excesses of diene relative to

aldehyde, the rate of both the reduction and desired coupling

are slow.

Figure 4. Kinetic profiles of the competing reductive coupling

and reduction processes as a function of diene concentration.

See the Supporting Information for experimental details.

■ CONCLUSION

In summary, we have developed a highly efficient copper-

catalyzed allylation of aldehydes using dienes as allylmetal sur-

rogates. Computational studies were performed which indicate

that a reversible isomerization of copper(I) allyl species is

formed, from which reaction of the trans-linear isomer with the

aldehyde yields the major stereoisomer of product. Transition

state models are provided, which show the specific steric inter-

actions between ligand and substrates that are responsible for

the stereoselectivity. Finally, kinetic experiments were per-

formed, demonstrating effect of aldehyde–diene relative con-

centration on the chemoselectivity of this reaction.

■ ASSOCIATED CONTENT

The Supporting Information is available free of charge on the

ACS Publications website at DOI: 10.1021/jacs.

Experimental procedures and characterization data for all

compounds (PDF)

NMR spectra (PDF)

SFC and HPLC traces (PDF)

Computational details and Cartesian coordinates of opti-

mized geometries (PDF)

■ AUTHOR INFORMATION

Corresponding Author

*[email protected]

ORCID

Chengxi Li: 0000-0003-3904-0299

Kwangmin Shin: 0000-0002-1708-2351

Richard Y. Liu: 0000-0003-0951-6487

Stephen L. Buchwald: 0000-0003-3875-4775

Author Contribution †These authors contributed equally.

Notes The authors declare no competing financial interest.

■ ACKNOWLEDGMENT

Research reported in this publication was supported by the Na-

tional Institutes of Health (GM122483, GM058160-17S1) and

Basic Science Research Program through the National Re-

search Foundation of Korea (NRF) funded by the Ministry of

Education (2018R1A6A3A03011441, K.S.).The content of this

communication solely reflects the research and opinion of the

authors and does not necessarily represent the official views of

the NIH. Solvias AG is acknowledged for a generous gift of SL-

J011-1 and Nippon Chemical is thanked for a kind donation of

(S,S)-QuinoxP*. We are grateful to Dr. Christine Nguyen for

advice on the preparation of this manuscript.

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Ruthenium‐Catalyzed C−C Bond‐Forming Transfer Hydrogen-

ation. Angew. Chem., Int. Ed. 2008, 47, 5220–5223. (d) Smejkal,

T.; Han, H.; Breit, B.; Krische, M. J. All-Carbon Quaternary

Centers via Ruthenium-Catalyzed Hydroxy-methylation of 2-

Substituted Butadienes Mediated by Formaldehyde: Beyond

Hydroformylation. J. Am. Chem. Soc. 2009, 131, 10366–10367.

(e) Zbieg, J. R.; Yamaguchi, E.; McInturff, E. L.; Krische, M.

J. Enantioselective C−H Crotylation of Primary Alcohols via

Hydrohydroxyalkylation of Butadiene. Science 2012, 336,

324–327. (f) Zbieg, J. R.; Moran, J.; Krische, M. J. Diastereo-

and Enantioselective Ruthenium-Catalyzed Hydrohydroxy-

alkylation of 2-Silyl-Butadienes: Carbonyl Syn-Crotylation

from the Alcohol Oxidation Level. J. Am. Chem. Soc. 2011, 133,

10582–10586. (g) Park, B. Y.; Montgomery, T. P.; Garza, V. J.;

Krische, M. J. Ruthenium Catalyzed Hydrohydroxyalkylation

of Isoprene with Heteroaromatic Secondary Alcohols: Isolation

and Reversible Formation of the Putative Metallacycle

Intermediate. J. Am. Chem. Soc. 2013, 135, 16320–16323. (h)

Nguyen, K. D.; Herkommer, D.; Krische, M. J. Ruthenium-

BINAP Catalyzed Alcohol C−H Tert-Prenylation via 1,3-

Enyne Transfer Hydrogenation: Beyond Stoichiometric

Carbanions in Enantioselective Carbonyl Propargylation. J. Am.

Chem. Soc. 2016, 138, 5238–5241.

(6) For selected examples of Ir-catalyzed reductive coupling of

π-unsaturated pronucleophiles with carbonyl compounds, see:

(a) Bower, J. F.; Patman, R. L.; Krische, M. J. Iridium-

Catalyzed C−C Coupling via Transfer Hydrogenation:

Carbonyl Addition from the Alcohol or Aldehyde Oxidation

Level Employing 1,3-Cyclohexadiene. Org. Lett. 2008, 10,

1033–1035. (b) Han, S. B.; Kim, I. S.; Han, H.; Krische, M. J.

Enantioselective Carbonyl Reverse Prenylation from the

Alcohol or Aldehyde Oxidation Level Employing 1,1-

Dimethylallene as the Prenyl Donor. J. Am. Chem. Soc. 2009,

131, 6916–6917. (c) Zbieg, J. R.; Fukuzumi, T.; Krische, M. J.

Iridium-Catalyzed Hydrohydroxyalkylation of Butadiene:

Carbonyl Crotylation. Adv. Synth. Catal. 2010, 352, 2416–2420.

(d) Geary, L. M.; Woo, S. K.; Leung, J. C.; Krische, M. J.

Diastereo- and Enantioselective Iridium-Catalyzed Carbonyl

Propargylation from the Alcohol or Aldehyde Oxidation Level:

1,3-Enynes as Allenylmetal Equivalents. Angew. Chem., Int. Ed.

2012, 51, 2972–2976. (e) Nguyen, K. D.; Herkommer, D.;

Krische, M. J. Enantioselective Formation of All-Carbon

Quaternary Centers via C–H Functionalization of Methanol:

Iridium-Catalyzed Diene Hydrohydroxymethylation. J. Am.

Chem. Soc. 2016, 138, 14210–14213. (f) Holmes, M.; Nguyen,

K. D.; Schwartz, L. A.; Luong, T.; Krische, M. J.

Enantioselective Formation of CF3-Bearing All-Carbon

Quaternary Stereocenters via C–H Functionalization of

Methanol: Iridium Catalyzed Allene Hydrohydroxymethylation.

J. Am. Chem. Soc. 2017, 139, 8114–8117. (g) Xiang, M.; Luo,

G.; Wang, Y.; Krische, M. J. Enantioselective Iridium-

Catalyzed Carbonyl Isoprenylation via Alcohol-Mediated

Hydrogen Transfer. Chem. Commun. 2019, 55, 981–984.

(7) For selected examples of Ni-catalyzed reductive coupling of

π-unsaturated pronucleophiles with carbonyl compounds, see:

(a) Miller, K. M.; Luanphaisarnnont, T.; Molinaro, C.; Jamison,

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Iwata, K.; Tamaru, Y. Regio- and Stereoselective Nickel-

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Chem. Soc. 2006, 128, 8559–8568. (e) Köpfer, A.; Sam, B.;

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or Nickel Catalyst: Hydrohydroxymethylation via Transfer

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1,3-dienes, see: Bareille, L.; Le Gendre, P.; Moïse, C. First

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775–777.

(9) For recent examples of Cu-catalyzed stereoselective

addition of π-unsaturated pronucleophiles to carbonyl

derivatives reported by our research group, see: (a) Yang, Y.;

Perry, I. B.; Buchwald, S. L. Copper-Catalyzed

Enantioselective Addition of Styrene-Derived Nucleophiles to

Imines Enabled by Ligand-Controlled Chemoselective

Hydrocupration. J. Am. Chem. Soc. 2016, 138, 9787–9790. (b)

Yang, Y.; Perry, I. B.; Lu, G.; Liu, P.; Buchwald, S. L. Copper-

Catalyzed Asymmetric Addition of Olefin-Derived

Nucleophiles to Ketones. Science 2016, 353, 144–150. (c) Liu,

R. Y.; Yang, Y.; Buchwald, S. L. Regiodivergent and

Diastereoselective CuH-Catalyzed Allylation of Imines with

Terminal Allenes. Angew. Chem., Int. Ed. 2016, 55, 14077–

14080. (d) Tsai, E. Y.; Liu, R. Y.; Yang, Y.; Buchwald, S. L. A

Regio- and Enantioselective CuH-Catalyzed Ketone Allylation

with Terminal Allenes. J. Am. Chem. Soc. 2018, 140, 2007–

2011. (e) Liu, R. Y.; Zhou, Y.; Yang, Y.; Buchwald, S. L. En-

antioselective Allylation Using Allene, a Petroleum Cracking

Byproduct. J. Am. Chem. Soc. 2019, 141, 2251–2256. (f) Li, C.;

Liu, R. Y.; Jesikiewicz, L. T.; Yang, Y.; Liu, P.; Buchwald, S.

L. CuH-Catalyzed Enantioselective Ketone Allylation with 1,3-

Dienes: Scope, Mechanism, and Applications. J. Am. Chem.

Soc. 2019, 141, 5062–5070.

(10) For selected reports by other research groups, see: (a)

Saxena, A.; Choi, B.; Lam, H. W. Enantioselective Copper-

Catalyzed Reductive Coupling of Alkenylazaarenes with

Ketones. J. Am. Chem. Soc. 2012, 134, 8428–8431. (b) Gui, Y.-

Y.; Hu, N.; Chen, X.-W.; Liao, L.; Ju, T.; Ye, J.-H.; Zhang, Z.;

Li, J.; Yu, D.-G. Highly Regio- and Enantioselective Copper-

Catalyzed Reductive Hydroxymethylation of Styrenes and 1,3-

Dienes with CO2. J. Am. Chem. Soc. 2017, 139, 17011–17014.

(c) Li, K.; Shao, X.; Tseng, L.; Malcolmson, S. J. 2-Azadienes

as Reagents for Preparing Chiral Amines: Synthesis of 1,2-

Amino Tertiary Alcohols by Cu-Catalyzed Enantioselective

Reductive Couplings with Ketones. J. Am. Chem. Soc. 2018,

140, 598–601. (d) Shao, X.; Li, K.; Malcolmson, S. J.

Enantioselective Synthesis of Anti-1,2-Diamines by Cu-

Catalyzed Reductive Couplings of Azadienes with Aldimines

and Ketimines. J. Am. Chem. Soc. 2018, 140, 7083–7087. (e)

Li, M.; Wang, J.; Meng, F. Cu-Catalyzed Enantioselective

Reductive Coupling of 1,3-Dienes and Aldimines. Org. Lett.

2018, 20, 7288–7292. (f) Fu, B.; Yuan, X.; Li, Y.; Wang, Y.;

Zhang, Q.; Xiong, T.; Zhang, Q. Copper-Catalyzed

Asymmetric Reductive Allylation of Ketones with 1,3-Dienes.

Org. Lett. 2019, 21, 3576–3580.

(11) (a) Chen, J.-X.; Daeuble, J. F.; Brestensky, D. M.; Stryker,

J. M. Highly Chemoselective Catalytic Hydrogenation of

Unsaturated Ketones and Aldehydes to Unsaturated Alcohols

Using Phosphine-Stabilized Copper(I) Hydride Complexes.

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Chrisman, W.; Noson, K. Hydrosilylation of Aldehydes and

Ketones Catalyzed by [Ph3P(CuH)]6. J. Organomet. Chem.

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Krishnamurthy, D.; Grier, M. C. Catalytic Asymmetric

Allylation Reactions. 3. Extension to Methallylstannane,

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Effect. J. Org. Chem. 1993, 58, 6543–6544. (c) Yanagisawa, A.;

Nakashima, H.; Ishiba, A.; Yamamoto, H. Catalytic

Asymmetric Allylation of Aldehydes Using a Chiral Silver(I)

Complex. J. Am. Chem. Soc. 1996, 118, 4723–4724. (d) Ogawa,

C.; Sugiura, M.; Kobayashi, S. Stereospecific, Enantioselective

Allylation of Α‐Hydrazono Esters by Using Allyltrichloro-

silanes with BINAP Dioxides as Neutral‐Coordinate

Organocatalysts. Angew. Chem., Int. Ed. 2004, 43, 6491–6493.

(e) Kotani, S.; Hashimoto, S.; Nakajima, M. Chiral Phosphine

Oxide BINAPO as a Lewis Base Catalyst for Asymmetric

Allylation and Aldol Reaction of Trichlorosilyl Compounds.

Tetrahedron 2007, 63, 3122–3132. (f) Zhang, Y.; Li, N.; Qu,

B.; Ma, S.; Lee, H.; Gonnella, N. C.; Gao, J.; Li, W.; Tan, Z.;

Reeves, J. T. et al. Asymmetric Methallylation of Ketones

Catalyzed by a Highly Active Organocatalyst 3,3′-F2-BINOL.

Org. Lett. 2013, 15, 1710–1713. (g) Silverio, D. L.; Torker, S.;

Pilyugina, T.; Vieira, E. M.; Snapper, M. L.; Haeffner, F.;

Hoveyda, A. H. Simple Organic Molecules as Catalysts for

Enantioselective Synthesis of Amines and Alcohols. Nature

2013, 494, 216.

(13) Colacot, T. J. A Concise Update on the Applications of

Chiral Ferrocenyl Phosphines in Homogeneous Catalysis

Leading to Organic Synthesis. Chem. Rev. 2003, 103, 3101–

3118.

(14) Smith, A. B.; Kim, W.-S.; Tong, R. Uniting Anion Relay

Chemistry with Pd-Mediated Cross Coupling: Design, Synthe-

sis and Evaluation of Bifunctional Aryl and Vinyl Silane Linch-

pins. Org. Lett. 2010, 12, 588–591.

(15) In general, away from equilibrium, the Gibbs free energy

of reaction ∆G differs from the standard free energy of reaction

∆G‡ by a quantity related to the reaction quotient Q:

∆G – ∆G‡ = RT ln Q

In our system of interest, the aldehyde concentration is presum-

ably maintained at a very low value, meaning that states involv-

ing free aldehyde are lowered in free energy relative to those

involving the aldehyde bound to the catalyst. Although this ef-

fect is not reflected in Figure 2, which shows only the standard

free energies, it is a useful mnemonic to associate the effect of

decreasing the steady-state aldehyde concentration with raising

the energies of the grey-highlighted states relative to the white

ones.

(16) (a) Kagan, H. B.; Dang, T.-P. Asymmetric Catalytic

Reduction with Transition Metal Complexes. I. Catalytic

System of Rhodium(I) with (-)-2,3-0-Isopropylidene-2,3-

Dihydroxy-1,4-Bis(Diphenylphosphino)Butane, a New Chiral

Diphosphine. J. Am. Chem. Soc. 1972, 94, 6429–6433. (b) Ka-

gan, H. B. In Asymmetric Catalysis; Morrison, J. D., Ed.; Aca-

demic Press: New York, 1985; Vol. 5, pp 1−339. (c) Whitesell,

J. K. C2-Symmetry and Asymmetric Induction. Chem. Rev.

1989, 89, 1581–1590. (d) Walsh, P.; Kowzlowski, M. Funda-

mentals of Asymmetric Catalysis; University Science Books:

Sausalito, CA, 2008.

(17) For an example of allylation of carbonyl compounds via

six-membered Zimmerman-Traxler transition state, see: (a)

Grayson, M. N.; Krische, M. J.; Houk, K. N. Ruthenium-

Catalyzed Asymmetric Hydrohydroxyalkylation of Butadiene:

The Role of the Formyl Hydrogen Bond in Stereochemical

Control. J. Am. Chem. Soc. 2015, 137, 8838–8850. For a review,

see: (b) Mejuch, T.; Gilboa, N.; Gayon, E.; Wang, H.; Houk, K.

N.; Marek, I. Axial Preferences in Allylation Reactions via the

Zimmerman–Traxler Transition State. Acc. Chem. Res. 2013,

46, 1659–1669.

Table of Contents Graphic:

download fileview on ChemRxivManuscript-final.pdf (1.00 MiB)



Supporting Information S 1

Engaging Aldehydes in CuH-Catalyzed Reductive Coupling Reactions:

Stereoselective Allylation from 1,3-Diene Pronucleophiles


Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts

02139, United States

*Correspondence to: [email protected].

Contents

I. General InformationS2

II. Preparation of Starting MaterialsS3

III. General Procedures for CuH-Catalyzed Aldehyde Allylation ReactionsS6

IV. Characterization Data for Allylation ProductsS7

V. Additional Experiment to Confirm the Absolute Configuration of Allylation

Product of Aliphatic Aldehydes with 1,3-Dienes S24

VI. Other Explored ExamplesS25

VII. General Procedure for Kinetics Experiments S26

VIII. Computational Studies S27

IX. References S67

mailto:[email protected]


I. General Information.

General reagent information. All reactions were performed under a nitrogen

atmosphere using the indicated method in the general procedures. Toluene and

tetrahydrofuran (THF) were purchased from J.T. Baker in CYCLE-TAINER® solvent

delivery kegs and purified by passage under argon pressure through two packed columns

of neutral alumina and copper(II) oxide. Copper(II) acetate was purchased from Strem

and used as received. 1,2-bis((2S,5S)2,5-diphenylphospholano)ethane ((S,S)-Ph-BPE) and

1,2-bis((2R,5R)2,5-diphenylphospholano)ethane ((R,R)-Ph-BPE) ligands were purchased

from Namena Corp. and stored in a nitrogen-filled glove box. JosiPhos ligand (R)-1-

{(SP)-2-[Bis[4-(trifluoromethyl)-phenyl]phosphino]ferrocenyl}ethyldi-tert-

butylphosphine (JosiPhos SL-J011-1) was a gift from Solvias and stored in a nitrogen-

filled glove box. (R)-DTBM-SEGPHOS was purchased from Takasago. (S,S)-QuinoxP*

was donated by Nippon Chemical Industrial Co., Ltd. and stored in a nitrogen-filled

glove box. Dimethoxy(methyl)silane (DMMS) was purchased from Tokyo Chemical

Industry Co. (TCI) and stored in a nitrogen-filled glove box for long term storage.

(Caution: Dimethoxy(methyl)silane (DMMS, CAS: 16881-77-9) is listed by several

vendors (TCI, Alfa Aesar) SDS or MSDS as H318, a category I Causes Serious Eye

Damage. Other vendors (Sigma-Aldrich, Gelest) list DMMS as H319, a category II Eye

Irritant. DMMS should be handled in a well-ventilated fumehood using proper

precaution as outlined for the handling of hazardous materials in prudent practices in the

laboratory.1 At the end of the reaction, ammonium fluoride in methanol should be

carefully added to the reaction mixture. The resulting reaction mixture should be stirred

for at least 30 min or the time indicated in the detailed reaction procedure. All other

solvents and commercial reagents were used as received from Alfa Aesar, Acros

Organics, Chem-Impex, Combi-blocks, Sigma-Aldrich, Strem or TCI, unless otherwise

noted. Flash column chromatography was performed using 40-63 µm silica gel

(SiliaFlash® F60 from Silicycle), or with the aid of a Biotage Isolera Automated Flash

Chromatography System using prepacked SNAP silica cartridges (10-100 g). Organic

solutions were concentrated under reduced pressure using a Buchi rotary evaporator.

General analytical information. All new compounds were characterized by NMR

spectroscopy, IR spectroscopy, elemental analysis or high-resolution mass spectrometry,

optical rotation (if applicable), and melting point analysis (if solids). 1H, 13C, 19F and 31P

NMR spectra were recorded in CDCl3 or C6D6 on a Bruker 400 or 500 MHz instrument.

Chemical shifts for 1H NMR are reported as follows: chemical shift in reference to

residual CHCl3 at 7.26 ppm (δ ppm), multiplicity (s = singlet, br s = broad singlet, d =

doublet, t = triplet, q = quartet, sex = sextet, sep = septet, ddd = doublet of double of

doublets, td = triplet of doublets, m = multiplet), coupling constant (Hz), and integration.

Chemical shifts for 13C NMR are reported in terms of chemical shift in reference to the

https://www.tcichemicals.com/eshop/en/us/commodity/D2100/

https://www.alfa.com/en/content/msds/USA/L16197.pdf

http://www.sigmaaldrich.com/catalog/product/aldrich/66612?lang=en&region=US&cm_sp=Insite-_-noResults_16881-77-9-_-noResults9-1

http://www.gelest.com/wp-content/uploads/product_msds/SIM6508.0-msds.pdf


CDCl3 solvent signal (77.16 ppm). IR spectra were recorded on a Thermo Scientific

Nicolet iS5 spectrometer (iD5 ATR, diamond) and are reported in terms of frequency

of absorption (cm-1). Melting points were measured on a Mel-Temp capillary melting

point apparatus. Optical rotations were measured using a Jasco P-1010 digital polarimeter.

Elemental analyses were performed by Atlantic Microlabs Inc., Norcross, GA. High-

resolution mass spectra were recorded on a JEOL AccuTOF LC-Plus 46 DART system

and on an Agilent Technologies 6545 Q-TOF LC/MS system. Achiral gas

chromatography (GC) analyses were performed on an Agilent 7890A gas chromatograph

with an FID detector using a J & W DB-1 column (10 m, 0.1 mm I.D.). Enantiomeric

ratios (er’s) were determined by chiral SFC analysis using a Waters Acquity UPC2

instrument, Agilent 1200 Series HPLC (high performance liquid chromatography) or

Agilent 7890A GC analysis using a chiral stationary phase. Specific columns and

analytical methods are provided in the experimental details for individual compounds; the

wavelengths of light used for chiral analyses are provided with the associated

chromatograms. Thin-layer chromatography (TLC) was performed on silica gel 60Å F254

plates (SiliaPlate from Silicycle) and visualized with UV light or potassium

permanganate stain. Preparatory thin-layer chromatography (Prep-TLC) was performed

on silica gel GF with UV 254 (20 x 20 cm, 1000 microns, catalog # TLG-R10011B-341

from Silicycle) and visualized with UV light. The syringe pumps (PHD 2000 and PHD

Ultra) were purchased from Harvard Apparatus. Isolated yields reported in Table 2 of the

manuscript reflect the average values from two independent runs.

II. Preparation/Acquistion of Starting Materials

Aldehydes. All aldehydes were purchased from Alfa Aesar, Acros Organics, Chem-

Impex, Combi-blocks, Sigma-Aldrich or TCI and were used as received.

Preparation of 2-Substituted 1,3-Dienes. Dienes S1, S2 and S5-7 are known

compounds and were synthesized by a previously reported procedure.2

Preparation of Diene S3.2


- Step 1 (Synthesis of enol phosphate S3’)

An oven-dried 500 mL round bottom flask equipped with a magnetic stir bar was

evacuated and backfilled with argon. The flask was then charged with 3'-

fluoroacetophenone (6.1 mL, 50 mmol, 1.0 equiv) and anhydrous THF (180 mL). The

solution was cooled to -78 °C and LiHMDS (1.0 M in THF, 65 mL, 65 mmol, 1.3 equiv)

was added dropwise over 50 min via syringe pump. The resulting solution was allowed to

stir at -78 °C for 30 min. Diethyl chlorophosphate (10.9 mL, 75 mmol, 1.5 equiv) was

then added dropwise over 20 min via syringe pump and the reaction mixture was further

stirred at -78 °C for 3 h. The reaction mixture was allowed to warm to room temperature

and was quenched with sat. NH4Cl solution. The resulting mixture was transferred to a

separatory funnel and extracted with EtOAc (70 mL x 3). The combined organic layers

were dried over MgSO4, filtered, and concentrated under reduced pressure. The crude

product was purified by silica gel column chromatography (EtOAc/hexanes = 100/0 to

50/50) to afford the desired enol phosphate S3’ as an orange oil (7.5 g, 55% yield). 1H

NMR (500 MHz, CDCl3) δ 7.387.26 (m, 3H), 7.057.02 (m, 1H), 5.29 (dq, J = 12.8,

2.5 Hz, 2H), 4.25–4.17 (m, 4H), 1.35 (tt, J = 7.0, 1.3 Hz, 6H) ppm. 13C NMR (126 MHz,

CDCl3) δ: 162.8 (d, J = 245.4 Hz), 151.1 (dd, J = 7.8, 2.4 Hz), 136.6 (dd, J = 7.5, 7.5 Hz),

129.9 (d, J = 8.2 Hz), 120.9 (d, J = 3.0 Hz), 115.9 (d, J = 21.2 Hz), 112.3 (d, J = 23.6 Hz),

98.3 (d, J = 3.7 Hz), 64.6 (d, J = 6.0 Hz), 16.1 (d, J = 6.7 Hz) ppm. 19F NMR (471 MHz,

CDCl3) δ: -112.9 (m) ppm. 31P NMR (203 MHz, CDCl3) δ: -6.4 (m) ppm. IR: 2986,

1634, 1585, 1444, 1268, 1200, 1006, 918 cm-1. HRMS (ESI) Calcd. m/z for

[C12H16FO4P+H]+: 275.0843. Found: 275.0848.

- Step 2 (Synthesis of Diene S3)

An oven-dried 300 mL round bottom flask equipped with a magnetic stir bar was charged

with (dppe)NiCl2 (0.71 g, 1.35 mmol, 5 mol%). Then, the flask was evacuated and

backfilled with argon. Anhydrous THF (100 mL) was added and the resulting mixture

was cooled to 0 °C. Enol phosphate S3’ (7.4 g, 27 mmol, 1.0 equiv) was subsequently

added. Vinylmagesium bromide solution (1.0 M in THF, 30 mL, 30 mmol, 1.1 equiv)

was added dropwise over 40 min via syringe pump. The reaction mixture was warmed to

room temperature then stirred for 2 h. At this point the reaction mixture was cooled to

0 °C and quenched by the addition of sat. NH4Cl solution. The solution was then

transferred to a separatory funnel and extracted with Et2O (50 mL x 3). The combined

organic layers were dried over MgSO4, filtered, and concentrated under reduced pressure.

The crude product was purified by silica gel column chromatography (100% pentane as

an eluent) to afford the desired diene S3 as a colorless liquid (1.6 g, 41% yield). 1H NMR

(400 MHz, CDCl3) δ: 7.347.29 (m, 1H), 7.127.10 (m, 1H), 7.066.98 (m, 2H), 6.60

(dd, J = 17.4, 10.6 Hz, 1H), 5.335.18 (m, 4H) ppm. 13C NMR (101 MHz, CDCl3) δ:

162.6 (d, J = 245.4 Hz), 147.1 (d, J = 2.1 Hz), 142.0 (d, J = 7.6 Hz), 137.6, 129.6 (d, J =

8.3 Hz), 123.9 (d, J = 2.9 Hz), 117.4, 117.4, 115.2 (d, J = 21.7 Hz), 114.3 (d, J = 21.1 Hz)


ppm. 19F NMR (376 MHz, CDCl3) δ: -113.8 (m) ppm. IR: 2931, 2534, 2332, 1611, 1581,

1486, 1436, 1265, 1213, 992, 905, 782 cm-1. HRMS (DART) Calcd. m/z for

[C10H9F+H]+: 149.0761. Found: 149.0760.

Preparation of Diene S4.2

- Step 1 (Synthesis of enol phosphate S4’)

An oven-dried 500 mL round bottom flask equipped with a magnetic stir bar was

evacuated and backfilled with argon. The flask was then charged with 3-acetylthiophene

(4.4 g, 35 mmol, 1.0 equiv) and anhydrous THF (120 mL). The solution was cooled to -

78 °C and LiHMDS (1.0 M in THF, 46 mL, 46 mmol, 1.3 equiv) was added dropwise

over 40 min via syringe pump. The resulting solution was allowed to stir at -78 °C for 30

min. Diethyl chlorophosphate (7.6 mL, 53 mmol, 1.5 equiv) was then added dropwise

over 20 min via syringe pump and the reaction mixture was stirred at -78 °C for an

additional 3 h. The reaction mixture was warmed to room temperature and quenched with

sat. NH4Cl solution (c.a. 100 mL). The resulting mixture was transferred to a separatory

funnel and extracted with EtOAc (70 mL x 3). The combined organic layers were dried

over MgSO4, filtered, and concentrated under reduced pressure. The crude product was

purified by silica gel column chromatography (EtOAc/hexanes = 100/0 to 50/50) to

afford the desired enol phosphate S4’ as an orange oil (6.7 g, 73% yield). 1H NMR (400

MHz, CDCl3) δ: 7.467.45 (m, 1H), 7.287.26 (m, 1H), 7.217.19 (m, 1H), 5.155.13

(m, 2H), 4.254.15 (m, 4H), 1.35 (tt, J = 7.2, 1.4 Hz, 6H) ppm. 13C NMR (101 MHz,

CDCl3) δ: 148.7 (d, J = 7.5 Hz), 136.7 (d, J = 7.4 Hz), 126.3, 124.9, 122.6, 96.6 (d, J =

3.6 Hz), 64.5 (d, J = 6.1 Hz), 16.1 (d, J = 6.7 Hz) ppm. 31P NMR (162 MHz, CDCl3) δ: -

6.4 (m) ppm. IR: 2982, 1634, 1267, 1197, 1165, 999, 920, 795, 870 cm-1. HRMS (ESI)

Calcd. m/z for [C10H15O4PS+H]+: 263.0501. Found: 263.0503.

- Step 2 (Synthesis of Diene S4)

An oven-dried 300 mL round bottom flask equipped with a magnetic stir bar was charged

with (dppe)NiCl2 (0.63 g, 1.2 mmol, 4 mol%). Then, the flask was evacuated and

backfilled with argon. Anhydrous THF (90 mL) was added and the resulting mixture was

cooled to 0 oC. Enol phosphate S4’ (7.9 g, 30 mmol, 1.0 equiv) was subsequently added.

Vinylmagesium bromide solution (1.0 M in THF, 32 mL, 32 mmol, 1.05 equiv) was

added dropwise over 30 min via syringe pump. The reaction mixture was warmed to

room temperature and stirred for 1 h. At this point the reaction mixture was cooled to

0 °C and quenched with sat. NH4Cl solution (c.a. 40 mL). The solution was then

transferred to a separatory funnel and extracted with Et2O (60 mL x 3). The organic


layers were dried over MgSO4, filtered, and concentrated under reduced pressure. The

crude product was purified by silica gel column chromatography (100% pentane as an

eluent) to afford the desired diene S4 as a colorless liquid (1.7 g, 42% yield). All of the

spectroscopic data matched that reported in the literature.3

III. General Procedure for CuH-Catalyzed Aldehyde Allylation

Reactions.

In a nitrogen-filled glovebox, an oven-dried screw-cap reaction tube (Fisherbrand, 20 x

150 mm, catalog no. 1495937C) equipped with a stir bar was charged with Cu(OAc)2 (1.8

mg, 0.01 mmol, 1.0 mol %) and (S,S)-Ph-BPE (6.1 mg, 0.012 mmol, 1.2 mol %),

followed the addition of toluene (0.2 mL) via syringe (Note: addition of the exact amount

of copper catalyst and ligand is crucial for reaction efficiency). The reaction mixture was

stirred at room temperature for 3 min before the addition of the diene (2.0 mmol, 2.0

equiv) and DMMS (490 L, 4.0 mmol, 4.0 equiv), sequentially, via syringe. The reaction

vessel was capped (Cap: Kimble Chase Open Top S/T Closure catalog no. 73804-15425;

Septum: Thermo Scientific 1.3 mm silicone/PTFE catalog no. B7995-18) and removed

from the glovebox. The cap was wrapped in parafilm and the reaction tube was then

placed in an ice/water bath at 0 °C and stirring was commenced (Note: When R2 =

cyclohexyl or adamantyl, The reaction mixture was stirred at room temperature for 30

min before being placed in an ice/water bath at 0 °C). A stock solution of aldehyde was

prepared in a glovebox by dissolving 2.0 mmol of aldehyde in ca. 2 mL of toluene (1.0 M,

2 mL volumetric flask was used to prepare the stock solution, see Figure S1) Then, 1.0

mL of this aldehyde stock solution (1.0 mmol, 1.0 equiv) was slowly added to the

reaction vessel via syringe pump (addition rate - 5 μL/min). The resulting reaction

mixture was stirred at 0 °C (Note: the reaction temperature should be maintained at 0 °C

until the addition of the aldehyde is completed) and allowed to slowly warm to room

temperature overnight (18 h). After the reaction was completed as judged by GC-MS, a

saturated solution of NH4F in MeOH (ca. 10 mL) was carefully added to quench the

reaction (Caution: gas evolution was observed). The mixture was allowed to stir for 30

min at room temperature, diluted with EtOAc (ca. 15 mL), stirred for an additional 20

min at room temperature and then filtered through a short plug of Celite (2.0 cm) eluting

with additional EtOAc (ca. 20 mL). The solvent was removed under reduced pressure

with the aid of a rotary evaporator. At this point, the combined yield (of the

diastereomers) and the diastereomeric ratio (dr) were determined by 1H NMR

spectroscopic analysis using dibromomethane or 1,1,2,2-tetrachloroethane as an internal


standard (Note: The dr was determined by 1H NMR of the purified compound when it was

unable to be determined by 1H NMR of the unpurified reaction mixture due to the

complexity of the spectrum). The crude reaction mixture was purified by flash column

chromatography with the aid of a Biotage Isolera instrument to afford the desired product.

Enantiomeric ratios (er’s) were determined by chiral SFC analysis using a Waters

Acquity UPC2 instrument or HPLC or GC analysis using a chiral stationary phase.

Figure S1. Volumetric flask

IV. Characterization Data for Allylation Products.

(1S,2R)-1-(4-methoxyphenyl)-2-methyl-3-phenylbut-3-en-1-ol (1): The general

procedure was followed using 1.0 mL of a 1.0 M stock solution of 4-

methoxybenzaldehyde (136 mg, 1.0 mmol, 1.0 equiv) in toluene and buta-1,3-dien-2-

ylbenzene (260 mg, 2.0 mmol, 2.0 equiv). The crude reaction mixture was purified with

the aid of a Biotage Isolera system (25 g SNAP cartridge, 2% EtOAc/hexanes for 3

column volume (CV), then 2-5% EtOAc/hexanes for 10 CV, then 5-10% EtOAc/hexanes

for 5 CV, then 10-15% EtOAc/hexanes for 10 CV) to afford the title compound as a

colorless oil (220 mg, 82%), which slowly became a white solid after storing in a -20 °C

freezer. 1H NMR analysis [integration of methyl resonances at 1.11 (major) and 0.90

(minor) ppm] of the unpurified reaction mixture indicated a 12:1 dr. The absolute


configuration of the major stereoisomer was assigned as (1S,2R) by analogy with product

2.

Major diastereomer: 1H NMR (400 MHz, CDCl3) δ: 7.367.28 (m, 5H), 7.22 (d, J = 8.5

Hz, 2H), 6.84 (d, J = 8.9 Hz, 2H), 5.38 (s, 1H), 5.20 (s, 1H), 4.66 (d, J = 4.0 Hz, 1H),

3.79 (s, 3H), 3.10 (p, J = 6.7 Hz, 1H), 1.79 (br s, 1H), 1.11 (d, J = 7.0 Hz, 3H) ppm. 13C

NMR (101 MHz, CDCl3) δ: 158.7, 152.0, 142.5, 135.1, 128.5, 127.7, 127.2, 126.8, 114.2,

113.6, 74.1, 55.4, 45.7, 12.7 ppm. SFC analysis (AD-H column, scCO2/MeOH = 95/5 to

60/40, 2.5 mL/min) indicated a 95:5 er: tR (minor) = 4.85 min, tR (major) = 5.12 min.

Properties for mixture of diastereomers:

M.P. 5759 oC. IR: 3455 (-OH, broad), 2969, 2835, 1608, 1511, 1246, 1172, 1033, 905,

827, 774, 701 cm-1. [α]D24 = +74.1, (c = 1.00, CHCl3). Anal. Calcd. For C18H20O2: C,

80.56; H, 7.51. Found: C, 80.85; H, 7.45.

Duplicate experiment - Yield: 91%, 244 mg; dr: 11:1; er: 96:4. Average yield: 87%.

(1S,2R)-2-methyl-1,3-diphenylbut-3-en-1-ol (2): The general procedure was followed

using 1.0 mL of a 1.0 M stock solution of benzaldehyde (106 mg, 1.0 mmol, 1.0 equiv) in

toluene and buta-1,3-dien-2-ylbenzene (260 mg, 2.0 mmol, 2.0 equiv). The crude reaction

mixture was purified with the aid of a Biotage Isolera system (25 g SNAP cartridge, 2%

EtOAc/hexanes for 3 CV, then 2-5% EtOAc/hexanes for 10 CV, then 5-10%

EtOAc/hexanes for 10 CV) to afford the title as a colorless oil (209 mg, 88%). 1H NMR

analysis [integration of methyl resonances at 1.13 (major) and 0.95 (minor) ppm] of the

unpurified reaction mixture indicated a 5:1 dr. The absolute configuration of the major

stereoisomer was assigned as (1S,2R) by comparison of the specific optical rotation of the

isolated major diastereomer with the reported specific rotation value.4

Major diastereomer: 1H NMR (400 MHz, CDCl3) δ: 7.42 (m, 9H), 7.29 (m,

1H), 5.44 (s, 1H), 5.26 (s, 1H), 4.74 (d, J = 3.6 Hz, 1H), 3.18 (dt, J = 10.6, 5.3 Hz, 1H),

1.88 (br s, 1H), 1.13 (d, J = 6.9 Hz, 3H) ppm. 13C NMR (101 MHz, CDCl3) δ: 151.8,

142.8, 142.2, 128.5, 128.1, 127.6, 127.0, 126.7, 125.9, 114.2, 74.0, 45.4, 12.1 ppm. SFC

analysis (OJ-H column, scCO2/MeOH = 95/5 to 60/40, 2.5 mL/min) indicated a 94:6 er: tR

(minor) = 3.65 min, tR (major) = 4.37 min. [α]D23 = +56.9, (c = 2.00, C6D6).



IR: 3457 (-OH, broad), 3024, 2972, 1492, 1447, 1059, 1021, 978, 905, 755, 701 cm-1.

[α]D24 = +67.0, (c = 1.00, CHCl3). HRMS (DART) Calcd. m/z for [C17H18O-OH]+:

221.1325. Found: 221.1329.


(3R,4R)-4-methyl-1,5-diphenylhex-5-en-3-ol (3): The general procedure was followed

using 1.0 mL of a 1.0 M stock solution of 3-phenylpropanal (134 mg, 1.0 mmol, 1.0

equiv) in toluene and buta-1,3-dien-2-ylbenzene (260 mg, 2.0 mmol, 2.0 equiv). The

crude reaction mixture was purified with the aid of a Biotage Isolera system (25 g SNAP

cartridge, 100% hexanes for 1 CV, then 0-8% EtOAc/hexanes for 4 CV, then 8%

EtOAc/hexanes for 10 CV) to afford the title compound as a colorless oil (174 mg, 65%). 1H NMR analysis [integration of methyl resonances at 1.27 (major) and 1.21 (minor) ppm]

of the unpurified reaction mixture indicated a 9:1 dr. The absolute configuration of the

major stereoisomer was assigned as (3R,4R) by analogy.

Major diastereomer: 1H NMR (400 MHz, CDCl3) δ: 7.407.29 (m, 7H), 7.247.20 (m,

3H), 5.42 (s, 1H), 5.17 (s, 1H), 3.64m 2.952.80 (m, 2H), 2.702.62 (m,

1H), 1.911.85 (m, 2H), 1.64 (br s, 1H), 1.27 (d, J = 6.9 Hz, 3H) ppm. 13C NMR (101

MHz, CDCl3) δ: 152.3, 142.3, 142.2, 128.5, 128.4, 128.4, 127.6, 126.7, 125.8, 113.7,

72.1, 43.3, 36.5, 32.7, 13.2 ppm. SFC analysis (OD-H column, scCO2/MeOH = 95/5 to

60/40, 2.5 mL/min) indicated a 98:2 er: tR (minor) = 4.42 min, tR (major) =4.85 min.


IR: 3434 (-OH, broad), 3085, 3057, 3024, 2932, 1625, 1494, 1452, 1269, 1030, 900, 779,

748, 699 cm-1. [α]D24 = +89.1, (c = 1.00, CHCl3). HRMS (DART) Calcd. m/z for

[C19H22O-OH]+: 249.1638. Found: 249.1645.



(3R,4R,6S)-3,6,10-trimethyl-2-phenylundeca-1,9-dien-4-ol (4): The general procedure

was followed using 1.0 mL of a 1.0 M stock solution of (S)-3,7-dimethyloct-6-enal (154

mg, 1.0 mmol, 1.0 equiv) in toluene and buta-1,3-dien-2-ylbenzene (260 mg, 2.0 mmol,

2.0 equiv). The crude reaction mixture was purified with the aid of a Biotage Isolera

system (25 g SNAP cartridge, 2% EtOAc/hexanes for 3 CV, then 2-5% EtOAc/hexanes

for 10 CV, then 5-10% EtOAc/hexanes for 10 CV ) to afford the title compound as a

clear oil (229 mg, 80%). 1H NMR analysis of the unpurified reaction mixture indicated a

>20:1 dr (resonances that are typical of the minor diastereomer could not be detected).

The absolute configuration of the major stereoisomer was assigned as (3R,4R,6S) by

analogy.

Major diastereomer: 1H NMR (400 MHz, CDCl3) δ: 7.357.27 (m, 5H), 5.36 (s, 1H),

5.12 (s, 1H), 5.07 (t, J = 6.8 Hz, 1H), 3.63 (dt, J = 8.6, 3.8 Hz, 1H), 2.79 (qd, J = 6.8, 3.7

Hz, 1H), 2.031.88 (m, 2H), 1.67 (s, 3H), 1.58 (s, 3H), 1.631.48 (m, 2H), 1.35 (br s,

1H), 1.321.09 (m, 3H), 1.20 (d, J = 7.0 Hz, 3H), 0.83 (d, J = 6.5 Hz, 3H) ppm. 13C

NMR (101 MHz, CDCl3) δ: 152.6, 142.5, 131.2, 128.5, 127.6, 126.7, 124.9, 113.5, 70.3,

43.8, 42.3, 37.8, 29.5, 25.9, 25.6, 19.3, 17.8, 13.3 ppm. Chiral GC analysis

(HYDRODEX -3 P, 25 m*0.25 mm, initial: Value: 100 °C, hold 20 min; Ramp 1: rate:

0.3 °C/min, value: 160 °C, hold 20 min; Ramp 2: rate: 0.5 °C/min, value: 220 °C, hold 20

min) indicated a 98.5:1.5 er (dr): tR (minor) = 283.89 min, tR (major) = 289.87 min.


IR: 3445 (-OH, broad), 2958, 2922, 1620, 1490, 1449, 1374, 1089, 1023, 966, 895, 774,

699 cm-1. [α]D24 = +72.9, (c = 1.00, CHCl3). Anal. Calcd. For C20H30O: C, 83.86; H,

10.56. Found: C, 83.91; H, 10.72.

Duplicate experiment - Yield: 74%, 213 mg; er (dr): >20:1. Average yield: 77%.


(1R,2R)-1-cyclohexyl-2-methyl-3-phenylbut-3-en-1-ol (5): The general procedure was

followed using 1.0 mL of a 1.0 M stock solution of cyclohexanecarbaldehyde (112 mg,

1.0 mmol, 1.0 equiv) in toluene and buta-1,3-dien-2-ylbenzene (260 mg, 2.0 mmol, 2.0

equiv). The crude reaction mixture was purified with the aid of a Biotage Isolera system

(25 g SNAP cartridge, 2% EtOAc/hexanes for 3 CV, then 2-5% EtOAc/hexanes for 10

CV, 5-10% EtOAc/hexanes for 10 CV, then 10-15% EtOAc/hexanes for 5 CV) to afford

the title compound as a colorless oil (200 mg, 82%). 1H NMR analysis of the unpurified

reaction mixture indicated a >20:1 dr (resonances that are typical of the minor

diastereomer could not be detected). The absolute configuration of the major

stereoisomer was assigned as (1R,2R) by analogy.


5.16 (s, 1H), 3.123.03 (m, 2H), 1.991.93 (m, 1H), 1.771.61 (m, 4H), 1.501.40 (m,

2H), 1.331.03 (m, 3H), 1.16 (d, J = 6.7 Hz, 3H), 0.970.80 (m, 2H) ppm. 13C NMR

(101 MHz, CDCl3) δ: 152.7, 142.2, 128.5, 127.7, 126.7, 114.0, 75.9, 40.2, 39.5, 29.9,

29.1, 26.5, 26.3, 26.0, 11.7 ppm. SFC analysis (AD-H column, scCO2/MeOH = 95/5 to

60/40, 2.5 mL/min) indicated a 96:4 er: tR (major) = 3.45 min, tR (minor) = 3.55 min.


IR: 3479 (-OH, broad), 2920, 2849, 1442, 1257, 973, 900, 777, 699 cm-1. [α]D24 = +100.7,

(c = 1.00, CHCl3). Anal. Calcd. For C17H24O: C, 83.55; H, 9.90. Found: C, 83.55; H,

9.73.

Duplicate experiment - Yield: 81%, 199 mg; dr: >20:1; er: 98:2. Average yield: 82%.

(3S,4R)-2,2,4-trimethyl-5-phenylhex-5-en-3-ol (6): The general procedure was

followed using 1.0 mL of a 1.0 M stock solution of pivalaldehyde (86 mg, 1.0 mmol, 1.0

equiv) in toluene and buta-1,3-dien-2-ylbenzene (260 mg, 2.0 mmol, 2.0 equiv). The

crude reaction mixture was purified with the aid of a Biotage Isolera system (25 g SNAP

cartridge, 2% EtOAc/hexanes for 3 CV, then 2-5% EtOAc/hexanes for 10 CV, then 5-10%

EtOAc/hexanes for 10 CV) to afford the title compound as a colorless oil (198 mg, 91%). 1H NMR analysis [integration of tert-butyl resonances at 0.97 (major) and 0.94 (minor)

ppm] of the unpurified reaction mixture indicated a >20:1 dr. The absolute configuration

of the major stereoisomer was assigned as (3S,4R) by analogy.



5.19 (s, 1H), 3.24 (d, J = 2.1 Hz, 1H), 3.15 (q, J = 6.7 Hz, 1H), 1.54 (br s, 1H), 1.25 (d, J

= 6.9 Hz, 3H), 0.97 (s, 9H) ppm. 13C NMR (101 MHz, CDCl3) δ: 154.8, 142.5, 128.5,

127.6, 126.9, 113.2, 78.7, 39.3, 35.7, 27.3, 13.9 ppm. Chiral GC analysis (HYDRODEX

-3 P, 25 m*0.25 mm, initial: Value: 70 °C, hold 50 min; Ramp 1: rate: 1 °C/min, value:

100 °C, hold 10 min; Ramp 2: rate: 0.8 °C/min, value: 220 °C, hold 20 min) indicated a

>99.5:0.5 er: tR (minor) = 157.14 min, tR (major) =157.71 min.


IR: 3509 (-OH, broad), 2953, 2870, 1625, 1468, 1369, 1239, 1186, 1056, 973, 898, 779,

701 cm-1. [α]D24 = +57.9, (c = 1.00, CHCl3). Anal. Calcd. For C15H22O: C, 82.52; H,

10.16. Found: C, 82.76; H, 10.12.

Duplicate experiment - Yield: 83%, 182 mg; dr: >20:1; er: 99.5:0.5. Average yield: 87%.

(1S,2R)-3-(4-methoxyphenyl)-2-methyl-1-ferrocenylbut-3-en-1-ol (7): The general

procedure was followed using 1.0 mL of a 1.0 M stock solution of ferrocene-

carboxaldehyde (214 mg, 1.0 mmol, 1.0 equiv) in toluene and 1-(buta-1,3-dien-2-yl)-4-

methoxybenzene (320 mg, 2.0 mmol, 2.0 equiv). The crude reaction mixture was purified

with the aid of a Biotage Isolera system (25 g SNAP cartridge, 2% EtOAc/hexanes for 3

CV, then 2-5% EtOAc/hexanes for 10 CV, then 5-10% EtOAc/hexanes for 10 CV, then

10-10% EtOAc/hexanes for 5 CV) to afford the title compound as a red resin (321 mg,

85%). 1H NMR analysis [integration of methyl resonances at 1.20 (major) and 0.99


configuration of the major stereoisomer was assigned as (1S,2R) by analogy.

Major diastereomer: 1H NMR (400 MHz, CDCl3) δ: 7.26 (d, J = 8.7 Hz, 2H), 6.87 (d, J =

8.7 Hz, 2H), 5.29 (s, 1H), 5.08 (s, 1H), 4.41 (dd, J = 4.9, 1.9 Hz, 1H), 4.31 (d, J = 2.2 Hz,

1H), 4.204.11 (m, 8H), 3.84 (s, 3H), 2.902.79 (m, 1H), 2.02 (d, J = 2.1 Hz, 1H), 1.20

(d, J = 6.9 Hz, 3H) ppm. 13C NMR (101 MHz, CDCl3) δ: 159.1, 151.3, 135.2, 127.8,

113.7, 112.2, 92.8, 72.1, 69.4, 68.5, 68.5, 68.1, 67.7, 67.6, 65.5, 55.4, 45.4, 14.7 ppm.

SFC analysis (OD-H column, scCO2/MeOH = 95/5 to 60/40, 2.5 mL/min) indicated a

95.5:4.5 er: tR (minor) = 5.85 min, tR (major) = 6.43 min.



IR: 3559 (-OH, broad), 3083, 2972, 2901, 1610, 1506, 1454, 1239, 1182, 1106, 1033,

900, 836, 744 cm-1. [α]D23 = +15.9, (c = 1.00, CHCl3). HRMS (DART) Calcd. m/z for

[C22H24O2Fe]+: 376.1120. Found: 376.1128.


(1S,2R)-1-(furan-3-yl)-3-(4-methoxyphenyl)-2-methylbut-3-en-1-ol (8): The general

procedure was followed using 1.0 mL of a 1.0 M stock solution of furan-3-carbaldehyde

(96 mg, 1.0 mmol, 1.0 equiv) in toluene and 1-(buta-1,3-dien-2-yl)-4-methoxybenzene

(320 mg, 2.0 mmol, 2.0 equiv). The crude reaction mixture was purified with the aid of a

Biotage Isolera system (25 g SNAP cartridge, 2% EtOAc/hexanes for 3 CV, then 2-5%


EtOAc/hexanes for 5 CV) to afford the title compound as a light yellow oil (222 mg,

86%) . 1H NMR analysis [integration of methyl resonances at 1.20 (major) and 1.04




2H), 6.916.88 (m, 2H), 6.34 (t, J = 1.4 Hz, 1H), 5.36 (d, J = 1.1 Hz, 1H), 5.15 (t, J = 1.2

Hz, 1H), 4.69 (t, J = 3.5 Hz, 1H), 3.84 (s, 3H), 3.113.04 (m, 1H), 1.79 (d, J = 3.2 Hz,

1H), 1.20 (d, J = 7.0 Hz, 3H) ppm. 13C NMR (101 MHz, CDCl3) δ: 159.3, 150.8, 143.0,

139.5, 134.6, 127.8, 127.6, 113.9, 112.9, 108.8, 68.7, 55.4, 44.4, 13.1 ppm. SFC analysis

(OJ-H column, scCO2/MeOH = 95/5 to 60/40, 2.5 mL/min) indicated a 97:3 er: tR (minor)

= 3.85 min, tR (major) = 4.04 min.


IR: 3438 (-OH, broad), 2967, 2835, 1603, 1508, 1248, 1179, 1023, 831, 751 cm-1. [α]D23

= +60.9, (c = 1.00, CHCl3). HRMS (DART) Calcd. m/z for [C16H18O3-OH]+: 241.1223.

Found: 241.1231.



(1S,2R)-3-(3-fluorophenyl)-2-methyl-1-(thiophen-3-yl)but-3-en-1-ol (9): The general

procedure was followed using 1.0 mL of a 1.0 M stock solution of thiophene-3-

carbaldehyde (112 mg, 1.0 mmol, 1.0 equiv) in toluene and 1-(buta-1,3-dien-2-yl)-3-

fluorobenzene (296 mg, 2.0 mmol, 2.0 equiv). The crude reaction mixture was purified


CV, then 2-5% EtOAc/hexanes for 15 CV, then 5-10% EtOAc/hexanes for 10 CV) to

afford the title compound as a colorless oil (230 mg, 88%). 1H NMR analysis [integration

of methyl resonances at 1.19 (major) and 1.02 (minor ppm)] of the unpurified reaction

mixture indicated a 7:1 dr. The absolute configuration of the major stereoisomer was

assigned as (1S,2R) by analogy.


2H), 7.05-6.90 (m, 3H), 5.42 (s, 1H), 5.26 (s, 1H), 4.78 (d, J = 4.6 Hz, 1H), 3.08~3.15 (m,

1H), 1.90 (d, J = 2.4 Hz, 1H), 1.19 (d, J = 6.9 Hz, 3H) ppm. 13C NMR (101 MHz, CDCl3)

δ: 162.9 (d, J = 245.6 Hz), 150.6 (d, J = 2.0 Hz), 144.8 (d, J = 7.3 Hz), 144.4, 130.0 (d, J

= 8.5 Hz), 125.8, 125.8, 122.4 (d, J = 2.9 Hz), 121.0, 115.1, 114.4 (d, J = 21.3 Hz), 113.7

(d, J = 21.8 Hz), 72.2, 45.1, 13.4 ppm. 19F NMR (376 MHz, CDCl3) δ: -113.2 (m) ppm.

HPLC analysis (OD-H column, Hexane/IPA = 96/4, 0.8 mL/min) indicated a 97:3 er: tR

(major)= 13.11min, tR (minor) = 15.44 min.


IR: 3424 (-OH, broad), 3100, 2981, 1613, 1575, 1482, 1430, 1265, 1196, 1016, 902, 872,


[C15H15FOS-OH]+: 245.0795. Found: 245.0802.

Duplicate experiment - Yield: 81%, 213 mg; dr: 7:1; er: 97.5:2.5. Average yield: 85%.


tert-butyl 3-((1S,2R)-3-(3-fluorophenyl)-1-hydroxy-2-methylbut-3-en-1-yl)-1H-indole

-1-carboxylate (10): The general procedure was followed using using 2.0 mL of a 0.5 M

stock solution of tert-butyl 3-formyl-1H-indole-1-carboxylate (245 mg, 1.0 mmol, 1.0

equiv) in tetrahydrofuran and 1-(buta-1,3-dien-2-yl)-3-fluorobenzene (296 mg, 2.0 mmol,


system (25 g SNAP cartridge, 100% hexanes for 2 CV, then 0-12% EtOAc/hexanes for 5

CV, then 12% EtOAc/hexanes for 9 CV) to afford the title compound as a yellow resin

(310 mg, 79%). 1H NMR analysis [integration of methyl resonances at 1.18 (major) and

0.92 (minor) ppm] of the purified title compound indicated a 8:1 dr. The absolute


Major diastereomer: 1H NMR (400 MHz, C6D6) δ: 8.45 (br s, 1H), 7.64 (s, 1H), 7.52 (d,

J = 7.8 Hz, 1H), 7.277.22 (m, 1H), 7.167.12 (m, 1H), 6.956.91 (m, 1H), 6.856.82

(m, 2H), 6.746.69 (m, 1H), 5.11 (s, 1H), 5.04 (s, 1H), 4.77 (d, J = 4.6 Hz, 1H), 3.16 (p,

J = 6.9 Hz, 1H), 1.73 (s, 1H), 1.36 (s, 9H), 1.18 (d, J = 6.9 Hz, 3H) ppm. 13C NMR (101

MHz, C6D6) δ: 163.6 (d, J = 245.4 Hz), 151.5 (d, J = 2.0 Hz), 150.2, 145.8 (d, J = 7.2 Hz),

136.7, 130.3 (d, J = 8.4 Hz), 129.5, 125.1, 123.7, 123.7 (d, J = 7.1 Hz), 123.2, 123.0 (d, J

= 2.8 Hz), 120.3, 116.3, 115.2, 114.7 (d, J = 8.1 Hz), 114.5 (d, J = 8.7 Hz), 83.5, 70.2,

44.3, 28.2, 14.2 ppm. 19F NMR (471 MHz, C6D6) δ: -113.1 (m) ppm. HPLC analysis

(OD-H column, Hexane/IPA = 97/3, 0.8 mL/min) indicated a 99.5:0.5 er: tR (minor) =

12.23 min, tR (major) = 15.01 min.


IR: 3498 (-OH, broad), 2977, 2929, 1726, 1577, 1449, 1366, 1253, 1153, 1080, 1014,


[C24H26FNO3-OH]+: 378.1864. Found: 378.1864.

Duplicate experiment: Yield: 79%, 311 mg; dr: 8:1; er: 98.5:1.5. Average yield: 79%.

(1S,2R)-2-methyl-1-(4-(methylthio)phenyl)-3-(thiophen-3-yl)but-3-en-1-ol (11): The

general procedure was followed using 1.0 mL of a 1.0 M stock solution of 4-

(methylthio)benzaldehyde (152 mg, 1.0 mmol, 1.0 equiv) in toluene and 3-(buta-1,3-dien-

2-yl)thiophene (272 mg, 2.0 mmol, 2.0 equiv). The crude reaction mixture was purified




afford the title compound as a light yellow oil (261 mg, 90%). 1H NMR analysis

[integration of methyl resonances at 1.09 (major) and 0.96 (minor) ppm] of the unpurified

reaction mixture indicated a 6:1 dr. The absolute configuration of the major stereoisomer

was assigned as (1S,2R) by analogy.


5.17 (s, 1H), 4.77 (d, J = 3.8 Hz, 1H), 3.103.04 (m, 1H), 2.48 (s, 3H), 1.91 (s, 1H), 1.09

(d, J = 7.0 Hz, 3H) ppm. 13C NMR (101 MHz, CDCl3) δ: 145.8, 142.8, 139.9, 137.0,

126.6, 126.6, 126.3, 126.0, 120.7, 112.8, 77.6, 74.1, 45.5, 16.2, 12.3 ppm. HPLC

analysis (OD-H column, Hexane/IPA = 95/5, 0.8 mL/min) indicated a 94:6 er: tR (minor)

= 18.04 min, tR (major) = 20.26 min.


IR: 3457 (-OH, broad), 3107, 2979, 2915, 1620, 1492, 1400, 1260, 1089, 1009, 983, 902,

791 cm-1. [α]D23 = +61.4, (c = 1.00, CHCl3). HRMS (DART) Calcd. m/z for [C16H18OS2-

OH]+: 273.0766. Found: 273.0763.


(2R,3R)-3-methyl-4-(thiophen-3-yl)pent-4-en-2-ol (12): The general procedure was

followed using using 1.0 mL of a 1.0 M stock solution of acetaldehyde (44 mg, 1.0 mmol,

1.0 equiv) in toluene and 3-(buta-1,3-dien-2-yl)thiophene (272 mg, 2.0 mmol, 2.0 equiv).

The crude reaction mixture was purified with the aid of a Biotage Isolera system (25 g

SNAP cartridge, 2% EtOAc/hexanes for 3 CV, then 2-5% EtOAc/hexanes for 10 CV,

then 5-10% EtOAc/hexanes for 10 CV) to afford the title compound as a colorless oil

(156 mg, 86%). 1H NMR analysis [integration of resonances of two methyl groups at

1.23 (major, 3H), 1.24 (major, 3H) and 1.17 (minor, 3H x 2) ppm] of the unpurified

reaction mixture indicated a >20:1 dr. The absolute configuration of the major

stereoisomer was assigned as (2R,3R) by analogy.


2H), 5.51 (s, 1H), 5.11 (s, 1H), 3.903.84 (m, 1H), 2.792.72 (m, 1H), 1.57 (s, 1H), 1.24

(d, J = 6.3 Hz, 3H), 1.23 (d, J = 7.0 Hz, 3H) ppm. 13C NMR (101 MHz, CDCl3) δ: 146.5,

143.1, 126.3, 125.8, 120.6, 111.9, 69.2, 44.8, 20.9, 13.4 ppm. Chiral GC analysis

(HYDRODEX -3 P, 25 m*0.25 mm, initial: Value: 100 °C, hold 20 min; Ramp 1: rate:


0.3 °C/min, value: 160 °C, hold 20 min; Ramp 2: rate: 0.5 °C/min, value: 220 °C, hold 20

min) indicated a 99:1 er: tR (minor) = 131.24 min, tR (major) = 134.03 min.


IR: 3403 (-OH, broad), 3100, 2967, 2927, 1622, 1456, 1369, 1250, 1087, 898, 789 cm-1.

[α]D23 = +58.9, (c = 1.00, CHCl3). HRMS (ESI) Calcd. m/z for [C10H14OS+Na]+:

205.0658. Found: 205.0654.


(1R,2R)-1-cyclohexyl-2-methyl-3-(thiophen-3-yl)but-3-en-1-ol (13): The general

procedure was followed using 1.0 mL of a 1.0 M stock solution of

cyclohexanecarbaldehyde (112 mg, 1.0 mmol, 1.0 equiv) in toluene and 3-(buta-1,3-dien-

2-yl)thiophene (272 mg, 2.0 mmol, 2.0 equiv). The crude reaction mixture was purified


CV, then 2-5% EtOAc/hexanes for 10 CV, then 5-10% EtOAc/hexanes for 10 CV, then

10-10% EtOAc/hexanes for 5 CV) to afford the title as a colorless oil (206 mg, 82%). 1H

NMR analysis [integration of vinylic resonances at 5.33 (major) and 5.25 (minor) ppm]

of the unpurified reaction mixture indicated a >20:1 dr. The absolute configuration of the


Major diastereomer: 1H NMR (400 MHz, C6D6) δ: 6.98 (dd, J = 5.0, 1.5 Hz, 1H),

6.916.83 (m, 2H), 5.33 (d, J = 1.0 Hz, 1H), 4.96 (d, J = 1.1 Hz, 1H), 3.19 (dd, J = 8.1,

3.3 Hz, 1H), 2.882.82 (m, 1H), 2.16 (d, J = 12.8 Hz, 1H), 1.701.63 (m, 2H), 1.601.50

(m, 2H), 1.50 (m, 1H), 1.29 (s, 1H), 1.21 (m, 3H), 1.10 (d, J = 6.9 Hz, 3H),

0.920.80 (m, 2H) ppm. 13C NMR (101 MHz, C6D6) δ: 147.4, 143.5, 126.8, 126.1, 121.0,

112.4, 76.7, 41.0, 40.2, 30.3, 29.9, 27.2, 27.0, 26.7, 12.7 ppm. HPLC analysis (AD-H

column, Hexane/IPA = 96/4, 0.8 mL/min) indicated a 94:6 er: tR (minor) = 11.30 min, tR

(major) = 12.37 min.


IR: 3476 (-OH, broad), 3100, 2922, 2849, 1625, 1449, 1255, 1087, 973, 890, 786 cm-1.

[α]D23 = +61.8, (c = 1.00, CHCl3). HRMS (DART) Calcd. m/z for [C15H22OS-OH]+:

233.1359. Found: 233.1370.



tert-butyl 3-((3R,4R)-4-hydroxy-3-methylpent-1-en-2-yl)-1H-indole-1-carboxylate

(14): The general procedure was followed using 1.0 mL of a 1.0 M stock solution of

acetaldehyde (44 mg, 1.0 mmol, 1.0 equiv) in toluene and tert-butyl 3-(buta-1,3-dien-2-

yl)-1H-indole-1-carboxylate (539 mg, 2.0 mmol, 2.0 equiv). The crude reaction mixture

was purified with the aid of a Biotage Isolera system (25 g SNAP cartridge, 2%


EtOAc/hexanes for 10 CV, then 20-30% EtOAc/hexanes for 10 CV) to afford the title

compound as a colorless resin (286 mg, 91%). 1H NMR analysis [integration of vinylic

resonances at 5.34 (major) and 5.39 (minor) ppm] of the unpurified reaction mixture

indicated a 13:1 dr. The absolute configuration of the major stereoisomer was assigned as

(3R,4R) by analogy.


7.9 Hz, 1H), 7.58 (s, 1H), 7.36 (ddd, J = 8.4, 7.2, 1.3 Hz, 1H), 7.29 (td, J = 7.4, 7.0, 1.1

Hz, 1H), 5.57 (s, 1H), 5.34 (s, 1H), 3.893.83 (m, 1H), 2.692.77 (m, 1H), 1.71 (s, 9H),

1.57 (s, =1H), 1.29 (d, J = 6.9 Hz, 3H), 1.23 (d, J = 6.3 Hz, 3H) ppm. 13C NMR (101

MHz, CDCl3) δ: 149.8, 144.4, 135.8, 129.4, 124.7, 123.0, 122.9, 122.7, 120.4, 115.5,

114.1, 84.1, 69.3, 46.3, 28.3, 21.0, 13.3 ppm. HPLC analysis (OD-H column,

Hexane/IPA = 95/5, 0.8 mL/min) indicated a 99:1 er: tR (major) = 7.22 min, tR (minor) =

7.94 min.


IR: 3431 (-OH, broad), 2974, 2932, 1729, 1625, 1447, 1362, 1250, 1156, 1061, 917, 763,

744 cm-1. [α]D23 = +22.5, (c = 1.00, CHCl3). HRMS (DART) Calcd. m/z for

[C19H25NO3+H]+: 316.1907. Found: 316.1917



(3R,4S)-5-((E)-benzylidene)-2-cyclohexyl-3-methyldec-1-en-4-ol (15): The general

procedure was followed (Note: The reaction mixture was stirred at room temperature for

30 min before placed in an ice/water bath at 0 °C) using 1.0 mL of a 1.0 M stock solution

of (E)-2-benzylidene-heptanal (202 mg, 1.0 mmol, 1.0 equiv) in toluene and buta-1,3-

dien-2-ylcyclohexane (272 mg, 2.0 mmol, 2.0 equiv). The crude reaction mixture was

purified with the aid of a Biotage Isolera system (25 g SNAP cartridge, 100% hexanes for

2 CV, then 0-8% EtOAc/hexanes for 5 CV, then 8% EtOAc/hexanes for 5 CV) to afford

the title compound as a colorless oil (280 mg, 82%). 1H NMR analysis [integration of

allylic resonances at 4.25 (major) and 4.08 (minor) ppm] of the unpurified reaction

mixture indicated a 10:1 dr. The absolute configuration of the major stereoisomer was

assigned as (3R,4S) by analogy.

Major diastereomer: 1H NMR (400 MHz, C6D6) δ: 7.347.31 (m, 2H), 7.21 (t, J = 7.7 Hz,

2H), 7.09 (m, 1H), 6.93 (s, 1H), 4.95 (s, 1H), 4.93 (s, 1H), 4.26 (m, 1H),

2.59 (m, 2H), 2.09 (m, 1H), 1.89 (m, 2H), 1.741.68 (m, 3H), 1.63

(m, 2H), 1.56 (m, 2H), 1.261.14 (m, 7H), 1.17 (d, J = 7.0 Hz, 3H), 1.091.01 (m,

2H), 0.840.80 (m, 3H) ppm. 13C NMR (101 MHz, C6D6) δ: 158.9, 143.6, 139.3, 129.5,

128.9, 126.9, 126.3, 109.1, 75.1, 45.4, 42.9, 34.5, 33.3, 32.7, 29.8, 29.2, 27.8, 27.5, 27.0,

23.1, 14.5, 13.9 ppm. SFC analysis (OD-H column, scCO2/MeOH = 95/5 to 60/40, 2.5

mL/min) indicated a 95:5 er: tR (major) = 3.28 min, tR (minor) = 3.37 min.


IR: 3486 (-OH, broad), 2924, 2849, 1643, 1449, 1113, 886, 748, 694 cm-1. [α]D23 = -1.32,

(c = 1.00, CHCl3). HRMS (DART) Calcd. m/z for [C24H36O-OH]+: 323.2733. Found:

323.2740.



(2R,3R)-4-cyclohexyl-3-methylpent-4-en-2-ol (16): The general procedure was

followed (Note: The reaction mixture was stirred at room temperature for 30 min before

placed in an ice/water bath at 0 °C) using 1.0 mL of a 1.0 M stock solution of

acetaldehyde (44 mg, 1.0 mmol, 1.0 equiv) in toluene and buta-1,3-dien-2-ylcyclohexane

(272 mg, 2.0 mmol, 2.0 equiv). The crude reaction mixture was purified with the aid of a

Biotage Isolera system (25 g SNAP cartridge, 2% EtOAc/hexanes for 2 CV, then 2-5%


EtOAc/hexanes for 5 CV) to afford the title compound as a colorless oil (96 mg, 53%). 1H NMR analysis [integration of vinylic resonances at 4.76 (major) and 4.82 (minor) ppm]

of the unpurified reaction mixture indicated a >20:1 dr. The absolute configuration of the


Major diastereomer: 1H NMR (400 MHz, CDCl3) δ: 4.87 (s, 1H), 4.76 (s, 1H), 3.73 (p, J

= 6.1 Hz, 1H), 2.10 (qd, J = 6.9, 4.9 Hz, 1H), 1.821.61 (m, 7H), 1.30 (m, 4H),

1.17 (d, J = 6.3 Hz, 3H), 1.08 (m, 1H) 1.04 (d, J = 6.9 Hz, 3H) ppm. 13C NMR (101

MHz, CDCl3) δ: 158.9, 107.7, 69.2, 45.7, 44.9, 33.7, 32.6, 27.1, 26.9, 26.4, 20.9, 14.3.

Chiral GC analysis (HYDRODEX -3 P, 25 m*0.25 mm, initial: Value: 100 °C, hold 20

min; Ramp 1: rate: 0.3 °C/min, value: 160 °C, hold 20 min; Ramp 2: rate: 0.5 °C/min,

value: 220 °C, hold 20 min) indicated a 94:6 er: tR (minor) = 87.99 min, tR (major) = 90.42

min.


IR: 3377 (-OH, broad), 2977, 2927, 2853, 1636, 1440, 1366, 1262, 1080, 1025, 883, 751

cm-1. [α]D23 = +8.1, (c = 1.00, CHCl3). HRMS (ESI) Calcd. m/z for [C12H22O+H]+:

183.1743. Found: 183.1745.



(1R,2R)-3-cyclohexyl-1-cyclopropyl-2-methylbut-3-en-1-ol (17): The general



of cyclopropanecarbaldehyde (70 mg, 1.0 mmol, 1.0 equiv) in toluene and buta-1,3-dien-

2-ylcyclohexane (272 mg, 2.0 mmol, 2.0 equiv). The crude reaction mixture was purified

with the aid of a Biotage Isolera system (25 g SNAP cartridge, 100% hexanes for 2 CV,

then 0-7% EtOAc/hexanes for 5 CV, then 7% EtOAc/hexanes for 7 CV) to afford the title

compound as a clear oil (144 mg, 69%). 1H NMR analysis [integration of vinylic


indicated a 15:1 dr. The absolute configuration of the major stereoisomer was assigned as

(1R,2R) by analogy.

Major diastereomer: 1H NMR (400 MHz, CDCl3) δ: 4.89 (s, 1H), 4.81 (s, 1H), 2.81 (dd,

J = 8.2, 4.3 Hz, 1H), 2.35 (qd, J = 7.0, 4.1 Hz, 1H), 1.851.63 (m, 7H), 1.281.16 (m,

4H), 1.12 (d, J = 7.0 Hz, 3H), 1.05 (m, 2H), 0.56 (m, 2H), 0.36 (m, 1H),

0.220.16 (m, 1H) ppm. 13C NMR (101 MHz, CDCl3) δ: 158.6, 107.9, 77.6, 45.0, 44.2,

33.7, 32.4, 27.1, 26.9, 26.5, 15.5, 14.3, 3.4, 2.8. Chiral GC analysis (HYDRODEX -3 P,

25 m*0.25 mm, initial: Value: 100 °C, hold 20 min; Ramp 1: rate: 0.3 °C/min, value:

160 °C, hold 20 min; Ramp 2: rate: 0.5 °C/min, value: 220 °C, hold 20 min) indicated a

97:3 er: tR (minor) = 145.42 min, tR (major) = 145.93 min.


IR: 3422 (-OH, broad), 3081, 2929, 2856, 1639, 1447, 1260, 1011, 978, 888, 751 cm-1.

[α]D24 = +35.9, (c = 1.00, CHCl3). HRMS (ESI) Calcd. m/z for [C14H24O-OH]+:

191.1794. Found: 191.1792.

Duplicate experiment -Yield: 62%, 130 mg; dr: 14:1; er: 97:3. Average yield: 66%.

(1R,2R)-3-cyclohexyl-1-cyclopentyl-2-methylbut-3-en-1-ol (18): The general



of cyclopentanecarbaldehyde (98 mg, 1.0 mmol, 1.0 equiv) in toluene and buta-1,3-dien-

2-ylcyclohexane (272 mg, 2.0 mmol, 2.0 equiv). The crude reaction mixture was purified




afford the title compound as a colorless oil (138 mg, 58%). 1H NMR analysis [integration

of methyl resonances at 1.00 (major) and 0.96 (minor) ppm] of the unpurified reaction

mixture indicated a >20:1 dr. The absolute configuration of the major stereoisomer was

assigned as (1R,2R) by analogy.

Major diastereomer: 1H NMR (400 MHz, CDCl3) δ: 4.93 (s, 1H), 4.82 (s, 1H), 3.24 (dd,

J = 8.5, 2.9 Hz, 1H), 2.32 (qd, J = 7.1, 2.9 Hz, 1H). 1.971.52 (m, 15H), 1.42 (m,

6H), 1.00 (d, J = 7.0 Hz, 3H) ppm. 13C NMR (101 MHz, CDCl3) δ: 159.0, 108.1, 76.2,

44.6, 43.1, 42.2, 34.1, 32.6, 30.6, 29.2, 27.2, 26.9, 26.5, 25.8, 25.6, 12.2 ppm. Chiral GC

analysis (HYDRODEX -3 P, 25 m*0.25 mm, initial: Value: 70 °C, hold 50 min; Ramp

1: rate: 1.0 °C/min, value: 100 °C, hold 10 min; Ramp 2: rate: 0.8 °C/min, value: 220 °C,

hold 20 min) indicated a 95:5 er: tR (minor) = 179.01 min, tR (major) = 179.58 min.


IR: 3486 (-OH, broad), 2924, 2858, 1639, 1449, 1262, 1070, 969, 890, 753 cm-1. [α]D24 =

+25.2, (c = 1.00, CHCl3). HRMS (DART) Calcd. m/z for [C16H28O+H]+: 237.2213.

Found: 237.2220.

Duplicate experiment: Yield: 56%, 133 mg; dr: >20:1; er: 95:5. Average yield: 57%.

(3S,4R)-5-((3R,5R,7R)-adamantan-1-yl)-2,2,4-trimethylhex-5-en-3-ol (19): The

general procedure was followed (Note: The reaction mixture was stirred at room

temperature for 30 min before placed in an ice/water bath at 0 °C) using 1.0 mL of a 1.0

M stock solution of pivalaldehyde (86 mg, 1.0 mmol, 1.0 equiv) in toluene and

(3R,5R,7R)-1-(buta-1,3-dien-2-yl)adamantane (377 mg, 2.0 mmol, 2.0 equiv). The crude

reaction mixture was purified with the aid of a Biotage Isolera system (25 g SNAP

cartridge, 2% EtOAc/hexanes for 3 CV, then 2-5% EtOAc/hexanes for 10 CV, then 5-10%


compound as a white solid (145 mg, 52%). 1H NMR analysis of the unpurified reaction

mixture indicated a >20:1 dr (resonances that are typical of the minor diastereomer could

not be detected). The absolute configuration of the major stereoisomer was assigned as

(3S,4R) by analogy.


1.2 Hz, 1H), 3.17 (d, J = 1.3 Hz, 1H), 2.74 (q, J = 6.9 Hz, 1H), 2.032.00 (m, 3H),


1.741.63 (m, 13H), 1.05 (d, J = 7.0 Hz, 3H), 1.00 (s, 9H) ppm. 13C NMR (101 MHz,

CDCl3) δ: 165.6, 107.3, 80.5, 41.0, 39.1, 37.1, 36.4, 33.6, 28.7, 27.6, 16.6 ppm. Chiral

GC analysis (HYDRODEX -3 P, 25 m*0.25 mm, initial: Value: 100 °C, hold 20 min;

Ramp 1: rate: 0.3 °C/min, value: 160 °C, hold 20 min; Ramp 2: rate: 0.5 °C/min, value:

220 °C, hold 20 min) indicated a 99.5:0.5 er: tR (major) = 264.69 min, tR (minor) = 267.85

min.


M.P. 64-66 oC. IR: 3531 (-OH, broad), 2908, 2846, 1632, 1447, 1359, 1267, 1113, 1063,

966, 902, 765 cm-1. [α]D24 = +10.4, (c = 1.00, CHCl3). HRMS (DART) Calcd. m/z for

[C19H32O-OH]+: 259.2420. Found: 259.2419.

Duplicate experiment - Yield: 44%, 121 mg; dr: >20:1; er: 99.5:0.5. Average yield: 48%.

(1S,2R)-1-adamantan-1-yl)-2,7-dimethyl-3-methyleneoct-6-en-1-ol (20): The general

procedure was followed using 1.0 mL of a 1.0 M stock solution of adamantane-1-

carbaldehyde (164 mg, 1.0 mmol, 1.0 equiv) in toluene and myrcene (272 mg, 2.0 mmol,


system (25 g SNAP cartridge, 2% EtOAc/hexanes for 3 CV, then 2-5% EtOAc/hexanes

for 10 CV, then 5-10% EtOAc/hexanes for 10 CV, then 10-10% EtOAc/hexanes for 5 CV)

to afford the title compound as a colorless oil (227 mg, 75%). 1H NMR analysis

[integration of allylic resonances at 3.04 (major) and 2.93 (minor) ppm] of the unpurified

reaction mixture indicated a 5:1 dr. The absolute configuration of the major stereoisomer

was assigned as (1S,2R) by analogy.


4.83 (s, 1H), 3.03 (d, J = 2.0 Hz, 1H), 2.502.43 (m, 1H), 2.19 (m, 5H), 1.73

(m, 15H), 1.69 (s, 3H), 1.61 (s, 3H), 1.06 (d, J = 7.0 Hz, 3H) ppm. 13C NMR (101 MHz,

CDCl3) δ: 155.2, 131.8, 124.2, 108.9, 80.0, 39.4, 39.1, 37.3, 35.6, 28.7, 28.6, 26.8, 25.8,

17.9, 14.2 ppm. Chiral GC analysis (HYDRODEX -3 P, 25 m*0.25 mm, initial: Value:

100 °C, hold 20 min; Ramp 1: rate: 0.2 °C/min, value: 160 °C, hold 20 min; Ramp 2: rate:

0.4 °C/min, value: 220 °C, hold 20 min) indicated a 85:15 er: tR (minor)= 433.81 min, tR

(major) = 435.00 min.



IR: 3514 (-OH, broad), 2972, 2901, 2851, 1634, 1445, 1378, 1106, 985, 888, 817, 760

cm-1. [α]D23 = +7.2, (c = 1.00, CHCl3). HRMS (DART) Calcd. m/z for [C21H34O-OH]+:

285.2577. Found: 285.2588.

Duplicate experiment: Yield: 71%, 216 mg; dr: 5:1; er: 85:15. Average yield: 73%.

V. Additional Experiment to Confirm the Absolute Configuration of

Allylation Product of Aliphatic Aldehydes with Dienes

To confirm the absolute configuration of the products of allylation of aliphatic aldehydes

with dienes, allylation of pentanal with 2-phenyl-1,3-butadiene was conducted under the

standard reaction conditions. The absolute configuration of the major diastereomer of the

product is (3R, 4R) by comparison of NMR and specific optical rotation value from the

literature.4

(3R,4R)-3-methyl-2-phenyloct-1-en-4-ol (P1): The general procedure was followed

using 1.0 mL of a 1.0 M stock solution of pentanal (86 mg, 1.0 mmol, 1.0 equiv) in

toluene and buta-1,3-dien-2-ylbenzene (260 mg, 2.0 mmol, 2.0 equiv). The crude reaction

mixture was purified with the aid of a Biotage Isolera system (25 g SNAP cartridge, 0%


compound as a colorless oil (167 mg, 76%). 1H NMR analysis [integration of methyl


indicated a 14:1 dr.

Major diastereomer: 1H NMR (400 MHz, CDCl3) δ: 7.377.27 (m, 5H), 5.37 (d, J = 1.1

Hz, 1H), 5.14 (dd, J = 1.2, 1.2 Hz, 1H), 3.533.48 (m, 1H), 2.882.82 (m, 1H),

1.521.24 (m, 7H), 1.19 (d, J = 7.0 Hz, 3H), 0.88 (t, J = 7.0 Hz, 3H) ppm. 13C NMR

(101 MHz, CDCl3) δ: 152.4, 142.3, 128.4, 127.5, 126.6, 113.4, 72.2, 42.8, 34.3, 28.4,


22.7, 14.0, 12.5 ppm. SFC analysis (AD-H column, scCO2/MeOH = 95/5 to 60/40, 2.5

mL/min) indicated a 98.5:1.5 er: tR (major) = 2.67 min, tR (minor) = 2.80 min.


IR: 3443 (-OH, broad), 2956, 2931, 2872, 1493, 1459, 1443, 1270, 1074, 899, 777 cm-1.

[α]D23 = +95.9, (c = 1.09, CHCl3). HRMS (DART) Calcd. m/z for [C15H22O-OH]+:

201.1638. Found: 201.1642.

NMR and specific optical rotation value in the literature4: 1H NMR (500 MHz, CDCl3) δ: 7.377.28 (m, 5H), 5.37 (d, J = 1.0 Hz, 1H), 5.14 (d, J =

1.0 Hz, 1H), 3.50 (m, 1H), 2.85 (m, 1H), 1.86 (br s, 1H), 1.201.51 (m, 6H), 1.04 (d, J =

6.5 Hz, 3H), 0.89 (t, J = 7.0 Hz, 3H) ppm. 13C NMR (125 MHz, CDCl3) δ: 152.6, 142.5,

128.6, 127.7, 126.8, 113.7, 72.4, 43.0, 34.5, 28.7, 22.9, 14.2, 12.7 ppm. [α]D25 = +65.6, (c

= 1.09, CHCl3).

VI. Other Explored Examples


VII. General Procedure for Kinetics Experiments

In a nitrogen-filled glovebox, five oven-dried screw-cap reaction tubes (Fisherbrand, 20 x

150 mm, catalog no. 1495937C), each equipped with stir bars, were charged with

Cu(OAc)2 (1.8 mg, 0.01 mmol, 2.0 mol %) and (S,S)-Ph-BPE (5.1 mg, 0.01 mmol, 2.0

mol %), followed the addition of dry toluene (0.2 mL) via syringe. After the reaction

mixtures were stirred at room temperature for 3 min, the diene (indicated equiv) and

DMMS (245 μL, 2.0 mmol, 4.0 equiv) were added to each tube via syringe. The reaction

vessels were capped (Cap: Kimble Chase Open Top S/T Closure catalog no. 73804-

15425; Septum: Thermo Scientific 1.3 mm silicone/PTFE catalog no. B7995-18) and

removed from the glovebox. The caps were wrapped in parafilm and the reaction tubes

were then placed in a rt water bath and stirred. Benzaldehyde (51 μL, 0.5 mmol, 1.0 equiv)

was added to each tube quickly via a glass microsyringe, and a timer was started. After

the indicated time, according to the quenching schedule shown below, a saturated

solution of NH4F in MeOH (ca. 5 mL) was carefully added to quench one of the reactions

(Caution: gas evolution was observed). The mixture was allowed to stir for 30 min at

room temperature, diluted with EtOAc (ca. 10 mL), stirred for an additional 20 min at

room temperature and then filtered through a short plug of Celite (2.0 cm) eluting with

additional EtOAc (ca. 10 mL). The solvent was removed under reduced pressure with the

aid of a rotary evaporator. At this point, the reaction mixture was analyzed by 1H NMR

spectroscopic analysis using 1,1,2,2-tetrachloroethane as an internal standard. The yield

of product represents the combined yield of the two diastereomers, which were formed

with roughly 5:1 dr.

0 equiv diene 1 equiv diene 5 equiv diene

Time (min)

Reduction (%)

SM (%)

Reduction (%)

Product (%)

SM (%)

Reduction (%)

Product (%)

SM (%)

0 0 100 0 0 100 0 0 100

5 56 44

10 78 22

15 90 10 42 3 55 13 5 82

30 100 0 65 5 30 30 11 59

60 81 8 11 51 15 34

90 88 10 2 64 21 15

180 100 0 89 11 0 65 33 2


VIII. Computational Studies

Computational Details. All reported calculations were performed using the ORCA

software5 or GAUSSIAN 036. Images of the 3D structures were rendered using

CYLView.7 The geometry of all reactants and transition states were optimized using the

B3LYP functional in the gas phase. In these geometry optimizations, a mixed basis set of

SDD for Cu and 6-31G(d) for all other atoms was used. Ground and transition state

geometries were validated by vibrational analysis at the same level, showing zero and one

imaginary frequencies respectively. Single point energies were calculated using the M06-

2X8,9 functional on a mixed basis set of SDD for Cu and 6-311+G(d,p) for all other atoms.

In these energy calculations, the SMD solvation model10 with toluene as solvent was

applied. The reported Gibbs free energies and enthalpies include zero-point and thermal

corrections calculated at 298 K using B3LYP/SDD–6-31G(d).

Cartesian Coordinates and Calculated Thermodynamic Parameters for Optimized

Structures

LCuH (I) Charge: 0

Multiplicity: 1

Imaginary Frequencies: 0

Electronic Energy (B3LYP/6-31G(d)-SDD(Cu)): -2197.962326

Gibbs Free Energy (B3LYP/6-31G(d)-SDD(Cu)): -2197.415915

Electronic Energy (M06-2X/6-311+G(d,p)-SDD(Cu)/SMD(toluene)): -

2197.801093

Total Gibbs Free Energy: -2197.254682

Geometry:

P 0.91624 -1.34014 0.05164

C 0.11148 -3.06361 -0.13559

C 1.24485 -3.99333 -0.61602

C 2.53054 -3.53502 0.08225

C 2.67830 -2.01458 -0.17445

H 1.00707 -5.04232 -0.40020

H 1.38185 -3.91269 -1.70166

H 3.41456 -4.07303 -0.28018

H 2.46118 -3.72170 1.16176

P -0.91617 1.34009 0.05158

C -0.11109 3.06338 -0.13608

C -1.24432 3.99323 -0.61660

C -2.53007 3.53530 0.08183

C -2.67813 2.01488 -0.17468

H -1.00630 5.04221 -0.40101

H -1.38145 3.91240 -1.70219

H -3.41399 4.07342 -0.28066

H -2.46064 3.72216 1.16131

H -0.11655 -3.33247 0.90334

H 2.92082 -1.88233 -1.23758

Cu -0.00055 0.00031 1.76199

C -0.63951 0.43109 -1.56906

H -0.62528 1.12401 -2.41907


H -1.51915 -0.21313 -1.68554

C 0.63931 -0.43148 -1.56913

H 0.11700 3.33243 0.90279

H -2.92047 1.88258 -1.23785

C 1.19310 3.06586 -0.90360

C 3.66558 2.96178 -2.26433

C 2.38165 2.74114 -0.22619

C 1.27259 3.34474 -2.27639

C 2.49668 3.29575 -2.94894

C 3.60332 2.68392 -0.89615

H 2.34432 2.52452 0.83934

H 0.37940 3.61388 -2.83236

H 2.53314 3.52318 -4.01139

H 4.50257 2.41780 -0.34798

H 4.61632 2.92415 -2.78932

C -3.75640 1.33506 0.64378

C -5.82731 0.13659 2.13362

C -3.61845 1.12743 2.02579

C -4.94712 0.92881 0.02459

C -5.97619 0.33636 0.76013

C -4.64410 0.53322 2.76181

H -2.69414 1.40249 2.52684

H -5.07108 1.08082 -1.04577

H -6.89258 0.03401 0.25925

H -4.51165 0.37369 3.82853

H -6.62446 -0.32629 2.70935

C 3.75636 -1.33459 0.64418

C 5.82689 -0.13587 2.13434

C 4.94740 -0.92881 0.02529

C 3.61788 -1.12634 2.02604

C 4.64335 -0.53202 2.76222

C 5.97628 -0.33623 0.76100

H 5.07175 -1.08127 -1.04496

H 2.69332 -1.40102 2.52685

H 4.51049 -0.37201 3.82882

H 6.89292 -0.03426 0.26035

H 6.62389 0.32710 2.71020

C -1.19273 -3.06639 -0.90307

C -3.66522 -2.96271 -2.26381

C -1.27219 -3.34535 -2.27586

C -2.38131 -2.74180 -0.22568

C -3.60300 -2.68478 -0.89564

C -2.49628 -3.29656 -2.94841

H -0.37894 -3.61438 -2.83181

H -2.34400 -2.52513 0.83983

H -4.50228 -2.41874 -0.34748

H -2.53272 -3.52405 -4.01084

H -4.61597 -2.92522 -2.78880

H -0.00058 -0.00166 3.31401

H 0.62493 -1.12446 -2.41908

H 1.51893 0.21273 -1.68585

TS1 Charge: 0

Multiplicity: 1






2543.327127


Geometry:

P -0.75622 0.06472 1.35905

C -0.22381 -1.13375 2.74351

C -1.21406 -0.88732 3.89669

C -2.58938 -0.65206 3.25971

C -2.42640 0.45589 2.18890

H -1.22151 -1.73165 4.59720

H -0.93107 0.00366 4.47186

H -3.34509 -0.36010 3.99851

H -2.94603 -1.57550 2.78557

P 1.48852 1.09504 -0.83810

C 1.09865 2.56114 -2.00164

C 2.46276 3.06027 -2.52087

C 3.37830 1.83575 -2.64241

C 3.33317 1.10239 -1.27894

H 2.34577 3.58998 -3.47418

H 2.91473 3.76822 -1.81515

H 4.40865 2.11187 -2.89612

H 3.02080 1.16505 -3.43527

H -0.45772 -2.11463 2.31032

H -2.27467 1.40516 2.71955

Cu -0.19826 -0.48756 -0.78846

C 1.52627 1.75947 0.91453

H 1.89061 2.79386 0.93584

H 2.26831 1.13980 1.43133

C 0.17340 1.67088 1.64755

H 0.58755 2.06293 -2.83384

H 3.80575 1.77185 -0.54562

C 0.13759 3.57776 -1.42355

C -1.73205 5.36998 -0.29739

C -1.24488 3.34140 -1.52430

C 0.56157 4.73418 -0.75118

C -0.36343 5.62275 -0.19670

C -2.16974 4.22256 -0.96426

H -1.59364 2.44619 -2.03361

H 1.62088 4.95657 -0.66149

H -0.00962 6.51549 0.31294

H -3.23126 4.00665 -1.04703

H -2.45026 6.06210 0.13423

C 4.08665 -0.21530 -1.25254

C 5.62196 -2.58086 -1.27031

C 3.49018 -1.45176 -1.53745

C 5.46201 -0.18805 -0.96828

C 6.22564 -1.35504 -0.97898

C 4.25378 -2.62233 -1.54381

H 2.42097 -1.52844 -1.70954

H 5.93943 0.76212 -0.73530

H 7.28866 -1.30716 -0.75612

H 3.76506 -3.56993 -1.75413

H 6.21154 -3.49406 -1.27672

C -3.60834 0.62044 1.25910

C -5.85979 0.93937 -0.40591

C -4.36501 1.80043 1.28960


C -3.99796 -0.39762 0.37513

C -5.11250 -0.24038 -0.44838

C -5.48201 1.96125 0.46641

H -4.07831 2.60091 1.96864

H -3.42101 -1.31595 0.31338

H -5.38709 -1.04138 -1.12901

H -6.05746 2.88263 0.51195

H -6.72786 1.06116 -1.04848

C 1.25995 -1.11118 3.04001

C 4.04908 -1.05882 3.45814

C 1.81042 -0.41656 4.12680

C 2.13400 -1.78698 2.16919

C 3.51361 -1.75639 2.37154

C 3.19249 -0.39369 4.33572

H 1.16482 0.10495 4.82739

H 1.72583 -2.32365 1.31559

H 4.16761 -2.27255 1.67438

H 3.59626 0.14497 5.18949

H 5.12355 -1.03767 3.61981

H -1.15352 -0.70846 -2.06859

H 0.32028 1.84486 2.72060

H -0.49826 2.45514 1.27840

C -0.50958 -2.41102 -1.97087

O 0.37588 -2.56124 -1.05924

H -0.17877 -2.26094 -3.01078

C -1.84661 -3.08634 -1.86338

C -2.17764 -3.80346 -0.70734

C -2.74633 -3.06458 -2.93668

C -3.39926 -4.47332 -0.61874

H -1.45697 -3.83590 0.10404

C -3.96569 -3.73364 -2.85075

H -2.48939 -2.50842 -3.83606

C -4.29824 -4.43760 -1.68777

H -3.64750 -5.03120 0.28099

H -4.65691 -3.71095 -3.68957

H -5.24792 -4.96211 -1.62095

Copper alkoxide 11 Charge: 0

Multiplicity: 1





2543.375184


P -1.31942 -0.12779 -1.40115

C -0.61787 -0.54452 -3.13061

C -1.80414 -0.37155 -4.10259

C -2.65427 0.79288 -3.57923

C -2.96898 0.49760 -2.09147

H -1.44749 -0.19874 -5.12546

H -2.42196 -1.27799 -4.12752

H -3.58195 0.91761 -4.15022

H -2.09854 1.73631 -3.65908

P 0.18179 -1.05054 1.36540

C -0.70860 -1.04710 3.05472


C 0.07609 -2.05039 3.92385

C 1.55818 -1.90239 3.55668

C 1.66689 -2.03883 2.01765

H -0.10792 -1.87113 4.99019

H -0.23974 -3.07957 3.71190

H 2.18493 -2.65344 4.05162

H 1.92999 -0.91813 3.87013

H 0.07967 0.28290 -3.31069

H -3.65901 -0.35719 -2.06791

Cu 0.11114 0.86820 0.19045

C -0.68436 -2.33155 0.29751

H -1.08243 -3.14642 0.91438

H 0.10539 -2.75719 -0.33382

C -1.80282 -1.74686 -0.58989

H -0.49360 -0.04189 3.43788

H 1.45605 -3.08721 1.76696

C -2.21238 -1.18857 2.96291

C -5.01597 -1.36306 2.68199

C -2.98562 -0.04862 2.68035

C -2.87561 -2.41594 3.11035

C -4.26391 -2.50123 2.97429

C -4.36993 -0.13253 2.53467

H -2.49226 0.91392 2.56392

H -2.31524 -3.31659 3.34342

H -4.75609 -3.46224 3.10076

H -4.93929 0.76295 2.30212

H -6.09523 -1.43198 2.57574

C 3.01247 -1.67619 1.42633

C 5.54230 -1.05964 0.35176

C 3.49367 -0.35752 1.43043

C 3.82287 -2.67868 0.87450

C 5.07918 -2.37639 0.34421

C 4.74468 -0.04929 0.89516

H 2.88098 0.44376 1.83435

H 3.46738 -3.70709 0.86309

H 5.69376 -3.17056 -0.07270

H 5.08405 0.98234 0.89168

H 6.51650 -0.81996 -0.06609

C -3.61053 1.64466 -1.33519

C -4.89363 3.77341 -0.00825

C -4.99350 1.61928 -1.10055

C -2.87410 2.75466 -0.88825

C -3.51510 3.80672 -0.23085

C -5.63363 2.67318 -0.44554

H -5.57625 0.76401 -1.43761

H -1.79418 2.79738 -1.01125

H -2.92509 4.65093 0.11557

H -6.70729 2.63313 -0.27875

H -5.38621 4.59545 0.50471

C 0.17819 -1.82972 -3.18878

C 1.72700 -4.19203 -3.18048

C -0.38465 -3.06256 -3.55314

C 1.53649 -1.80652 -2.82669

C 2.30262 -2.97184 -2.81648

C 0.38257 -4.23043 -3.55200

H -1.42709 -3.12002 -3.85245

H 1.99531 -0.86150 -2.54432


H 3.34688 -2.92219 -2.52111

H -0.07486 -5.17176 -3.84602

H 2.32176 -5.10151 -3.18053

H 1.30201 3.05529 1.91017

H -2.11601 -2.49155 -1.33128

H -2.67818 -1.50902 0.02627

C 1.29365 3.42493 0.86411

H 0.92886 4.47135 0.93371

O 0.45833 2.69715 0.03163

C 2.74952 3.50259 0.40037

C 3.09486 3.21793 -0.92520

C 3.76362 3.89613 1.28477

C 4.41835 3.32700 -1.35883

H 2.30422 2.90932 -1.60218

C 5.08831 4.00802 0.85711

H 3.51190 4.11981 2.32103

C 5.42150 3.72309 -0.47086

H 4.66849 3.10329 -2.39386

H 5.86061 4.31607 1.55867

H 6.45158 3.81025 -0.80812

Reduction product VI Charge: 0

Multiplicity: 1





905.8988498


H 0.19071 -1.23226 -0.82542

C 0.47494 -0.77091 0.13191

H 0.33099 -1.53461 0.91155

C 1.93446 -0.36662 0.08089

C 2.38417 0.82215 0.66307

C 2.86384 -1.21900 -0.52879

C 3.74133 1.15171 0.63634

H 1.66317 1.48607 1.12766

C 4.22001 -0.89358 -0.55132

H 2.52395 -2.14353 -0.99242

C 4.66354 0.29579 0.03216

H 4.07786 2.08083 1.08948

H 4.92875 -1.56436 -1.03018

H 5.71906 0.55392 0.01200

O -0.35850 0.34528 0.41700

Si -2.01388 0.33465 0.27045

C -2.60584 1.92439 1.03729

H -3.68962 2.03027 0.92115

H -2.37691 1.93941 2.10824

H -2.12406 2.79610 0.58091

O -2.70787 -0.93572 1.05717

O -2.43574 0.15021 -1.32577

C -1.97182 0.99770 -2.36674

H -2.41363 2.00048 -2.28976

H -0.87852 1.09537 -2.35452

H -2.27431 0.56051 -3.32336

C -3.04541 -2.20616 0.51896


H -3.34817 -2.13228 -0.53109

H -2.19646 -2.89832 0.59667

H -3.87687 -2.61375 1.10293

Diene (1b), s-trans Charge: 0

Multiplicity: 1





195.264157


Geometry:

C 0.01013 0.23842 -0.09769

C 0.55537 -0.90601 -0.70416

C 1.92403 -1.16622 -0.63554

C 2.77366 -0.29262 0.04712

C 2.24400 0.84489 0.65875

C 0.87534 1.10698 0.58633

H -0.09761 -1.58435 -1.24534

H 2.32799 -2.05146 -1.12000

H 3.83922 -0.49864 0.10364

H 2.89540 1.52795 1.19783

H 0.46305 1.98584 1.07427

C -1.44447 0.55580 -0.20795

C -1.84295 1.77083 -0.63397

H -2.89698 2.02778 -0.70428

H -1.13044 2.53460 -0.92971

C -2.45587 -0.44903 0.16060

H -3.48176 -0.16347 -0.07233

C -2.24013 -1.62493 0.76659

H -1.24597 -1.96309 1.04205

H -3.06754 -2.28384 1.01338

Diene (1b), s-cis Charge: 0

Multiplicity: 1





195.259461


Geometry:

C 0.15827 0.18128 -0.00838

C 0.62383 -1.12312 0.23116

C 1.98979 -1.40491 0.25432

C 2.92031 -0.38888 0.02986

C 2.47260 0.91058 -0.22137

C 1.10765 1.19092 -0.24475

H -0.09339 -1.91706 0.42077

H 2.32681 -2.41945 0.45075

H 3.98461 -0.60810 0.04277

H 3.18855 1.70583 -0.41242

H 0.76779 2.19718 -0.47254


C -1.30217 0.47196 -0.00946

C -1.79212 1.65406 0.40972

H -2.85185 1.87932 0.34220

H -1.15200 2.42206 0.83334

C -2.20139 -0.59622 -0.50518

H -1.82874 -1.17720 -1.34920

C -3.39850 -0.89897 0.01089

H -3.78970 -0.38661 0.88621

H -4.02168 -1.67620 -0.42271

TS2a Charge: 0

Multiplicity: 1





2584.773009


Geometry:

P -0.89403 -1.08548 0.75199

C 0.43195 -1.98110 1.80492

C -0.30801 -3.13546 2.51324

C -1.38558 -3.64769 1.55201

C -2.21161 -2.42196 1.09793

H 0.39582 -3.92480 2.80453

H -0.79119 -2.78357 3.43318

H -2.03618 -4.39629 2.01985

H -0.91629 -4.12568 0.68262

P -0.45486 2.04656 -0.21054

C -1.89832 3.20209 -0.70157

C -1.43710 4.61605 -0.30591

C 0.04534 4.72073 -0.67507

C 0.77683 3.50610 -0.05090

H -2.04235 5.38465 -0.80291

H -1.54664 4.77138 0.77485

H 0.49486 5.65852 -0.32723

H 0.15645 4.70192 -1.76665

H 1.08120 -2.42022 1.03973

H -2.76346 -2.05678 1.97465

Cu -0.28974 -0.07792 -1.19560

C -0.76697 1.64525 1.59591

H -1.29569 2.46726 2.09425

H 0.22442 1.56727 2.05676

C -1.53770 0.32822 1.80185

H -1.89385 3.14368 -1.79810

H 0.87314 3.69060 1.02655

C -3.26057 2.74502 -0.22530

C -5.78436 1.80042 0.61902

C -3.91529 1.70994 -0.91650

C -3.90091 3.29949 0.89351

C -5.15106 2.83334 1.31004

C -5.15924 1.23916 -0.49798

H -3.42992 1.25774 -1.77787

H -3.43682 4.11186 1.44466

H -5.62975 3.28536 2.17521

H -5.63474 0.42904 -1.04342


H -6.75734 1.44018 0.94274

C 2.15880 3.25401 -0.61157

C 4.75701 2.85536 -1.63740

C 2.36468 3.00545 -1.97813

C 3.28043 3.29379 0.22833

C 4.56774 3.09647 -0.27637

C 3.64852 2.80994 -2.48720

H 1.51251 2.95803 -2.65198

H 3.14306 3.48254 1.29063

H 5.42180 3.13607 0.39493

H 3.78309 2.62049 -3.54896

H 5.75736 2.70518 -2.03428

C -3.21039 -2.69768 -0.00249

C -5.11342 -3.27977 -2.00008

C -4.57954 -2.50297 0.22754

C -2.81028 -3.18685 -1.25578

C -3.75162 -3.47620 -2.24313

C -5.52501 -2.79085 -0.75958

H -4.90981 -2.12533 1.19294

H -1.75418 -3.33138 -1.46276

H -3.41950 -3.85306 -3.20707

H -6.58193 -2.63889 -0.55477

H -5.84562 -3.50722 -2.77034

C 1.28378 -1.06988 2.66151

C 2.90157 0.68932 4.16982

C 0.94511 -0.72701 3.98076

C 2.45687 -0.51782 2.11794

C 3.25492 0.35267 2.86095

C 1.74428 0.14244 4.72670

H 0.05526 -1.14468 4.44299

H 2.74554 -0.77788 1.10366

H 4.15704 0.76058 2.41328

H 1.46195 0.38711 5.74769

H 3.52561 1.36151 4.75300

H -1.10128 -0.16571 -2.58249

H -1.52988 0.05635 2.86426

H -2.58509 0.45725 1.50551

C 3.24171 -2.35352 -1.31682

C 4.33549 -1.51709 -1.60516

C 5.58553 -1.73394 -1.02373

C 5.77799 -2.79205 -0.13411

C 4.70357 -3.63188 0.16718

C 3.45545 -3.41241 -0.41410

H 4.21081 -0.70000 -2.30865

H 6.41334 -1.07444 -1.27293

H 6.75066 -2.95855 0.32143

H 4.83419 -4.45574 0.86459

H 2.62392 -4.06337 -0.15959

C 1.90498 -2.13766 -1.95584

C 1.14562 -3.22302 -2.26665

H 0.16913 -3.12061 -2.72966

H 1.51546 -4.23395 -2.13440

C 1.52635 -0.75557 -2.25081

H 2.21390 0.02776 -1.95495

C 0.47991 -0.40947 -3.15254

H 0.08467 -1.18694 -3.80112

H 0.52726 0.56556 -3.63017


TS2b Charge: 0

Multiplicity: 1





2584.763902


Geometry:

C -2.75389 -3.21142 -1.31715

C -2.52742 -3.21271 0.07070

C -3.14752 -4.14617 0.90303

C -4.00494 -5.10907 0.36784

C -4.23271 -5.12956 -1.00957

C -3.61191 -4.19576 -1.83921

H -1.86518 -2.46624 0.49978

H -2.95924 -4.12076 1.97392

H -4.48448 -5.83853 1.01540

H -4.88899 -5.88080 -1.44222

H -3.77539 -4.23025 -2.91230

C -2.12641 -2.20705 -2.23402

C -2.90805 -1.62955 -3.18279

H -2.49343 -0.91670 -3.89189

H -3.96932 -1.84082 -3.26169

C -0.68950 -1.92670 -2.15479

H -0.30955 -1.32398 -2.97797

C 0.26645 -2.71700 -1.44412

H -0.08407 -3.61104 -0.93714

H 1.25792 -2.82462 -1.87224

P 1.71006 0.87472 -0.98793

C 1.44248 2.27216 -2.27499

C 2.85832 2.72814 -2.67714

C 3.73067 1.47387 -2.76464

C 3.56166 0.68786 -1.44150

H 2.83997 3.28710 -3.62114

H 3.27902 3.39819 -1.91740

H 4.78687 1.71514 -2.93421

H 3.40711 0.85675 -3.61218

P -0.54271 0.31838 1.37659

C -0.18074 -0.65240 2.99513

C -1.39259 -0.41114 3.92689

C -2.62173 -0.11847 3.05600

C -2.19537 0.97546 2.05081

H -1.54727 -1.27577 4.58353

H -1.21301 0.45143 4.57916

H -3.47625 0.21902 3.65460

H -2.94434 -1.01928 2.51686

H 1.00761 1.73782 -3.12984

H 4.10483 1.23212 -0.65829

Cu 0.17815 -0.80930 -0.46818

C 0.47843 1.88913 1.38246

H 0.63709 2.23878 2.40928

H -0.14605 2.63373 0.87515

C 1.83192 1.76112 0.66085

H -0.21901 -1.68978 2.64718

H -1.92594 1.86108 2.64446


C 1.19578 -0.42490 3.58223

C 3.80777 -0.03817 4.59137

C 2.25183 -1.27371 3.20703

C 1.47987 0.62127 4.47525

C 2.76967 0.81169 4.97596

C 3.54205 -1.08263 3.70280

H 2.05529 -2.08188 2.50767

H 0.68984 1.29440 4.79636

H 2.96006 1.62526 5.67144

H 4.33810 -1.75661 3.39690

H 4.81027 0.10785 4.98473

C -3.25969 1.39438 1.06058

C -5.33290 2.19979 -0.67304

C -3.63651 0.59330 -0.02751

C -3.93725 2.60747 1.25880

C -4.96785 3.00698 0.40654

C -4.66049 0.99415 -0.88697

H -3.12561 -0.34402 -0.21855

H -3.65718 3.24397 2.09590

H -5.48259 3.94770 0.58603

H -4.92168 0.35776 -1.72759

H -6.13376 2.50677 -1.34090

C 4.09215 -0.72862 -1.47621

C 5.15652 -3.34130 -1.54446

C 5.03340 -1.15022 -0.52679

C 3.69270 -1.64491 -2.46196

C 4.21971 -2.93579 -2.49843

C 5.56081 -2.44303 -0.55672

H 5.36010 -0.45515 0.24378

H 2.95836 -1.35052 -3.20763

H 3.89700 -3.62666 -3.27306

H 6.29159 -2.74432 0.18947

H 5.56689 -4.34699 -1.57335

C 0.46111 3.34605 -1.85852

C -1.42964 5.29851 -1.08081

C 0.86901 4.56832 -1.29996

C -0.91713 3.12475 -2.01765

C -1.85143 4.08809 -1.63547

C -0.06450 5.53402 -0.91611

H 1.92484 4.78487 -1.17124

H -1.27979 2.19495 -2.44884

H -2.91006 3.88225 -1.76191

H 0.28130 6.47435 -0.49395

H -2.15672 6.04975 -0.78443

H 0.92305 -2.17043 -0.00623

H 2.28469 2.75356 0.54358

H 2.51788 1.15619 1.26552

(S)-IIa Charge: 0

Multiplicity: 1





2584.828111



Geometry:

P -0.82876 -0.64975 1.11017

C 0.30141 -1.69133 2.25030

C -0.66160 -2.50154 3.14353

C -1.87611 -2.87197 2.28503

C -2.40503 -1.56326 1.64842

H -0.15724 -3.38672 3.55010

H -0.99916 -1.90319 3.99911

H -2.66545 -3.35871 2.87029

H -1.57923 -3.57462 1.49615

P 0.27263 2.04638 -0.37092

C -0.91536 3.37080 -1.07072

C -0.11905 4.68932 -1.02640

C 1.32315 4.35333 -1.42065

C 1.79512 3.18467 -0.51946

H -0.56552 5.44088 -1.68941

H -0.12282 5.11174 -0.01373

H 1.99456 5.21360 -1.31412

H 1.36055 4.04822 -2.47426

H 0.77081 -2.39234 1.55031

H -2.84074 -0.95923 2.45583

Cu -0.02010 -0.21570 -1.05171

C -0.00912 2.05753 1.48743

H -0.29675 3.05650 1.83767

H 0.96661 1.82590 1.93171

C -1.04790 1.01634 1.94664

H -1.01215 3.08003 -2.12481

H 1.96328 3.58848 0.48735

C -2.30085 3.35193 -0.46214

C -4.88663 3.19341 0.66096

C -3.23404 2.40510 -0.91969

C -2.69473 4.22241 0.56494

C -3.97548 4.14515 1.11924

C -4.50997 2.32097 -0.36396

H -2.95157 1.72143 -1.71745

H -2.00796 4.97796 0.93456

H -4.25916 4.83585 1.90932

H -5.20477 1.57038 -0.72940

H -5.88201 3.13488 1.09296

C 3.06898 2.50703 -0.97678

C 5.47922 1.31694 -1.82885

C 3.14498 1.83823 -2.20916

C 4.22060 2.56129 -0.17956

C 5.41615 1.97277 -0.59895

C 4.33753 1.25147 -2.63220

H 2.26118 1.76044 -2.83697

H 4.18164 3.07351 0.77940

H 6.29776 2.03295 0.03429

H 4.37312 0.73954 -3.59025

H 6.40792 0.85984 -2.15961

C -3.46025 -1.75523 0.57966

C -5.48027 -2.16057 -1.34422

C -4.78767 -1.38553 0.83977

C -3.15918 -2.33087 -0.66534

C -4.16064 -2.53048 -1.61610

C -5.79170 -1.58669 -0.11046

H -5.03864 -0.93777 1.79934


H -2.13926 -2.61340 -0.91473

H -3.89917 -2.97447 -2.57278

H -6.81508 -1.29783 0.11640

H -6.25795 -2.31823 -2.08698

C 1.40712 -0.91290 2.92834

C 3.50470 0.58787 4.08113

C 1.25506 -0.30580 4.18505

C 2.63860 -0.76174 2.26729

C 3.67366 -0.01687 2.83292

C 2.29274 0.43525 4.75593

H 0.32515 -0.41471 4.73580

H 2.78516 -1.24131 1.30238

H 4.61248 0.08677 2.29572

H 2.15186 0.88988 5.73337

H 4.31172 1.16305 4.52726

H -1.53669 -0.82026 -3.76659

H -1.02251 0.92119 3.03858

H -2.05555 1.34967 1.67086

C 1.34377 -3.27307 -1.60006

C 2.67384 -2.81503 -1.55548

C 3.61357 -3.39063 -0.69758

C 3.25013 -4.43643 0.15355

C 1.93295 -4.90061 0.13174

C 0.99759 -4.32474 -0.72948

H 2.98532 -2.00916 -2.21209

H 4.63673 -3.02175 -0.70039

H 3.98111 -4.88249 0.82298

H 1.63046 -5.71309 0.78869

H -0.02606 -4.68900 -0.72912

C 0.33057 -2.67840 -2.53349

C -0.57511 -3.51228 -3.10361

H -1.32287 -3.15011 -3.80181

H -0.57005 -4.58197 -2.91721

C 0.38083 -1.20868 -2.75997

H 1.42426 -0.90525 -2.92540

C -0.45786 -0.71799 -3.94611

H -0.24256 -1.27158 -4.87768

H -0.26832 0.34528 -4.14357

TS3-cis Charge: 0

Multiplicity: 1





2584.816747


Geometry:

C -2.04645 -2.97161 -1.59898

C -2.07836 -3.42244 -0.26670

C -3.12049 -4.22211 0.20386

C -4.16151 -4.59863 -0.64819

C -4.14378 -4.16736 -1.97551

C -3.09831 -3.36854 -2.44305

H -1.28177 -3.12152 0.40577

H -3.11959 -4.55240 1.24018


H -4.97183 -5.22427 -0.28307

H -4.94066 -4.46060 -2.65477

H -3.07827 -3.05521 -3.48257

C -0.93710 -2.12162 -2.14672

C -1.28463 -1.07351 -2.97292

H -0.52574 -0.51217 -3.51287

H -2.31968 -0.79629 -3.14138

C 0.45257 -2.38323 -1.75729

H 1.13448 -1.95306 -2.49803

C 0.93435 -3.77529 -1.36709

H 0.83824 -4.50585 -2.19000

H 1.99743 -3.73213 -1.10245

P 1.53384 1.20915 -0.82942

C 1.16648 2.73275 -1.93687

C 2.53957 3.35289 -2.25890

C 3.52656 2.19672 -2.44640

C 3.41053 1.28462 -1.20352

H 2.48034 3.99565 -3.14610

H 2.88468 3.98340 -1.43006

H 4.55809 2.54819 -2.56830

H 3.27296 1.63381 -3.35383

P -0.70036 0.09726 1.35212

C -0.24815 -1.01187 2.84931

C -1.37984 -0.81852 3.87886

C -2.68169 -0.62187 3.09306

C -2.42504 0.50684 2.06764

H -1.43260 -1.67387 4.56369

H -1.20126 0.07181 4.49447

H -3.52290 -0.36012 3.74596

H -2.95657 -1.54722 2.57030

H 0.78807 2.26833 -2.85652

H 3.84464 1.83203 -0.35649

Cu 0.16178 -0.68463 -0.64673

C 0.16657 1.73868 1.63080

H 0.27507 1.94494 2.70270

H -0.51663 2.49221 1.22130

C 1.53470 1.84509 0.93669

H -0.35335 -2.02050 2.43186

H -2.27324 1.43212 2.63985

C 1.18050 -0.86874 3.32647

C 3.88500 -0.61898 4.10411

C 2.19149 -1.60441 2.68306

C 1.55526 -0.00874 4.37047

C 2.89249 0.11336 4.75665

C 3.52764 -1.48011 3.06342

H 1.92510 -2.27207 1.86726

H 0.80263 0.56677 4.90134

H 3.15512 0.78040 5.57392

H 4.28669 -2.05702 2.54256

H 4.92425 -0.52571 4.40806

C -3.55214 0.75109 1.08929

C -5.73422 1.21479 -0.63488

C -3.94081 -0.21361 0.14764

C -4.27409 1.95211 1.14708

C -5.35686 2.18407 0.29592

C -5.02028 0.01595 -0.70552

H -3.39548 -1.14846 0.07183


H -3.98808 2.71314 1.87017

H -5.90636 3.11973 0.36523

H -5.29809 -0.74825 -1.42621

H -6.57702 1.39084 -1.29823

C 4.12615 -0.04286 -1.31204

C 5.52542 -2.48447 -1.50546

C 5.08917 -0.40028 -0.35771

C 3.87756 -0.93412 -2.36696

C 4.56832 -2.14152 -2.46400

C 5.78336 -1.60875 -0.45044

H 5.29939 0.27733 0.46693

H 3.12931 -0.68858 -3.11540

H 4.35477 -2.81749 -3.28750

H 6.53064 -1.86011 0.29818

H 6.06398 -3.42512 -1.58213

C 0.08547 3.65251 -1.41522

C -2.00249 5.28305 -0.43674

C 0.36134 4.79493 -0.64729

C -1.26012 3.34852 -1.68577

C -2.29311 4.14968 -1.20035

C -0.67157 5.60275 -0.16522

H 1.38816 5.07217 -0.42813

H -1.49674 2.46743 -2.27748

H -3.32351 3.88205 -1.41461

H -0.43128 6.48664 0.42041

H -2.80483 5.91324 -0.06234

H 0.40855 -4.20520 -0.50904

H 1.89422 2.88074 0.97668

H 2.26820 1.22511 1.46618

TS3-trans Charge: 0

Multiplicity: 1





2584.810655


Geometry:

P -0.30535 -1.48447 0.57906

C 0.67769 -2.03762 2.12138

C 0.06396 -3.39720 2.52067

C -0.29543 -4.13562 1.22532

C -1.15478 -3.17270 0.37327

H 0.76386 -3.96742 3.14321

H -0.84732 -3.25411 3.11444

H -0.84276 -5.06586 1.41777

H 0.61805 -4.40779 0.68181

P -1.61306 1.88559 -0.49296

C -3.43330 2.51407 -0.43282

C -3.39224 3.84924 0.33038

C -2.14885 4.59199 -0.16697

C -0.93866 3.62881 -0.05802

H -4.31103 4.42976 0.17385

H -3.30253 3.67970 1.41131

H -1.95958 5.51320 0.39761


H -2.29202 4.88822 -1.21418

H 1.67479 -2.23504 1.71086

H -2.12169 -3.06234 0.88166

Cu 1.04204 -0.56515 -0.93634

C -1.44117 1.08174 1.20503

H -2.11184 1.56309 1.92703

H -0.41959 1.27988 1.54839

C -1.71865 -0.43434 1.19634

H -3.64041 2.74768 -1.48631

H -0.63941 3.58592 0.99665

C -4.43762 1.47144 0.00139

C -6.26768 -0.55517 0.73957

C -4.83939 0.48286 -0.91571

C -4.98226 1.42381 1.29373

C -5.88705 0.42271 1.65831

C -5.73902 -0.51890 -0.55409

H -4.43653 0.50433 -1.92596

H -4.71360 2.18019 2.02479

H -6.29911 0.41465 2.66434

H -6.03435 -1.26605 -1.28642

H -6.97486 -1.33003 1.02296

C 0.26565 4.05796 -0.86917

C 2.50689 4.91207 -2.35362

C 0.20980 4.15390 -2.26866

C 1.46697 4.39510 -0.23149

C 2.57918 4.81728 -0.96380

C 1.31581 4.57763 -3.00383

H -0.70528 3.88190 -2.78977

H 1.53195 4.32702 0.85250

H 3.50014 5.07218 -0.44568

H 1.25032 4.64138 -4.08690

H 3.36977 5.23990 -2.92705

C -1.42394 -3.60477 -1.05150

C -1.97514 -4.42971 -3.68918

C -2.74402 -3.70812 -1.51261

C -0.38155 -3.91923 -1.93764

C -0.65511 -4.32836 -3.24275

C -3.01977 -4.11585 -2.81939

H -3.56505 -3.46595 -0.84086

H 0.65228 -3.82305 -1.61698

H 0.16695 -4.56431 -3.91338

H -4.05110 -4.19025 -3.15463

H -2.18588 -4.74857 -4.70637

C 0.83508 -0.98951 3.20272

C 1.18425 1.02340 5.15116

C -0.07888 -0.84024 4.25738

C 1.93473 -0.11528 3.15120

C 2.10635 0.88167 4.11139

C 0.09415 0.15556 5.22165

H -0.93026 -1.50948 4.34394

H 2.66650 -0.22590 2.35434

H 2.96759 1.54163 4.04980

H -0.62439 0.24713 6.03219

H 1.31932 1.79584 5.90346

H 1.32223 -0.41513 -3.91549

H -1.98407 -0.77288 2.20505

H -2.57610 -0.66771 0.55494


C 4.26110 -0.83542 -0.69303

C 5.14476 0.25698 -0.70495

C 6.16519 0.37046 0.24012

C 6.32074 -0.60029 1.23177

C 5.44728 -1.68981 1.26424

C 4.43204 -1.80318 0.31364

H 5.03973 1.01419 -1.47601

H 6.84303 1.21971 0.19928

H 7.11172 -0.50855 1.97169

H 5.55375 -2.45112 2.03351

H 3.75443 -2.65251 0.34371

C 3.19018 -0.96847 -1.73348

C 2.90977 -2.20443 -2.22644

H 2.15622 -2.34761 -2.99503

H 3.50802 -3.07187 -1.96438

C 2.41402 0.22614 -2.10500

H 2.84964 1.14802 -1.71963

C 1.97274 0.39318 -3.56093

H 2.83360 0.43269 -4.25184

H 1.40882 1.32531 -3.67538

IIb-cis Charge: 0

Multiplicity: 1





2584.831691


Geometry:

C -0.88416 3.57299 -1.41481

C -1.72952 3.74162 -0.30439

C -1.45282 4.69225 0.68225

C -0.31697 5.49869 0.58204

C 0.53266 5.34828 -0.51760

C 0.25195 4.39633 -1.49992

H -2.61480 3.11641 -0.22101

H -2.12803 4.80423 1.52768

H -0.10129 6.24224 1.34516

H 1.41221 5.98047 -0.61530

H 0.91344 4.29437 -2.35631

C -1.15877 2.52961 -2.45555

C -0.10374 1.48016 -2.61278

H -0.27401 0.91333 -3.53857

H 0.89016 1.94487 -2.68948

C -2.30708 2.54859 -3.17249

H -2.43005 1.75925 -3.91737

C -3.42555 3.55571 -3.12468

H -3.62765 3.96247 -4.12656

H -4.37448 3.11463 -2.77912

P -0.49617 -1.98326 -0.56847

C 0.47050 -3.23874 -1.64276

C -0.49485 -4.42294 -1.85834

C -1.90923 -3.84217 -1.96955

C -2.13005 -2.93681 -0.73252

H -0.21145 -4.99960 -2.74753


H -0.46217 -5.11286 -1.00591

H -2.67671 -4.62398 -2.01472

H -2.00451 -3.24562 -2.88635

P 1.01415 0.34493 1.12741

C 0.05213 1.29439 2.48257

C 1.13196 1.88516 3.41348

C 2.32362 2.28009 2.53425

C 2.69616 1.03902 1.68779

H 0.73303 2.73832 3.97580

H 1.46389 1.14227 4.14963

H 3.18446 2.61101 3.12764

H 2.04393 3.11340 1.87735

H 0.56310 -2.71042 -2.59969

H -2.19000 -3.59355 0.14605

Cu 0.03779 0.26447 -1.03551

C 1.13756 -1.43875 1.70928

H 1.21365 -1.49511 2.80192

H 2.08423 -1.80945 1.29728

C -0.02576 -2.32209 1.21685

H -0.38893 2.12748 1.92199

H 3.11640 0.28810 2.37031

C -1.07985 0.51694 3.11696

C -3.23589 -0.96342 4.18510

C -2.33827 0.51077 2.49037

C -0.92917 -0.22906 4.29635

C -1.99615 -0.95978 4.82556

C -3.40364 -0.22245 3.01235

H -2.47874 1.08657 1.57868

H 0.02266 -0.23777 4.81893

H -1.85528 -1.52463 5.74371

H -4.36051 -0.21651 2.49837

H -4.06454 -1.53228 4.59828

C 3.70049 1.28761 0.58422

C 5.62096 1.76008 -1.42521

C 3.43407 2.17878 -0.46826

C 4.94336 0.63935 0.60810

C 5.89761 0.87164 -0.38544

C 4.38532 2.41180 -1.46142

H 2.47377 2.68445 -0.52050

H 5.16877 -0.05238 1.41712

H 6.85720 0.36238 -0.34153

H 4.15782 3.10246 -2.26921

H 6.36016 1.94466 -2.20020

C -3.39097 -2.09805 -0.77940

C -5.79416 -0.62844 -0.88501

C -4.49995 -2.47361 -0.00749

C -3.50609 -0.96918 -1.60617

C -4.69554 -0.24120 -1.65629

C -5.69313 -1.74960 -0.05937

H -4.42839 -3.34519 0.64013

H -2.65653 -0.63743 -2.19706

H -4.75389 0.63552 -2.29494

H -6.54111 -2.06302 0.54459

H -6.71952 -0.05988 -0.92600

C 1.87025 -3.54049 -1.15405

C 4.50338 -3.97480 -0.22764

C 2.16997 -4.62310 -0.31294


C 2.92187 -2.68533 -1.52706

C 4.22182 -2.89382 -1.06716

C 3.47299 -4.83950 0.14287

H 1.38868 -5.31538 -0.01313

H 2.71409 -1.84302 -2.18343

H 5.01042 -2.20830 -1.36414

H 3.68019 -5.68968 0.78787

H 5.51606 -4.14471 0.12801

H -3.20084 4.39953 -2.46580

H 0.21460 -3.38060 1.37268

H -0.92900 -2.10107 1.79776

IIb-trans Charge: 0

Multiplicity: 1





2584.825574


Geometry:

P -1.35276 -0.20697 1.45782

C -0.47478 -0.27029 3.15616

C -1.58398 -0.60459 4.17474

C -2.55003 -1.57754 3.48967

C -2.96949 -0.93804 2.14294

H -1.15566 -1.02240 5.09412

H -2.13485 0.30024 4.46005

H -3.43251 -1.78920 4.10496

H -2.05087 -2.53760 3.30429

P 0.02044 1.41758 -1.01450

C -1.00677 1.80271 -2.58341

C -0.27442 2.96870 -3.28028

C 1.22765 2.77043 -3.04544

C 1.42973 2.58893 -1.52177

H -0.52774 3.00284 -4.34701

H -0.57625 3.93110 -2.84890

H 1.81922 3.61810 -3.41117

H 1.58212 1.87778 -3.57680

H 0.16442 -1.15762 3.06447

H -3.61546 -0.08026 2.37324

Cu -0.06405 -0.87247 -0.40447

C -0.76309 2.37991 0.39526

H -1.18516 3.32860 0.04214

H 0.06951 2.62327 1.06604

C -1.83418 1.58395 1.16606

H -0.85028 0.90479 -3.19369

H 1.19800 3.55135 -1.04560

C -2.49530 1.93741 -2.34807

C -5.27046 2.07911 -1.83967

C -3.29412 0.78061 -2.34950

C -3.12048 3.16802 -2.09420

C -4.49369 3.23831 -1.84543

C -4.66362 0.84636 -2.09368

H -2.83199 -0.18369 -2.54915

H -2.54065 4.08630 -2.09884


H -4.95529 4.20473 -1.65898

H -5.25199 -0.06680 -2.09029

H -6.33834 2.13591 -1.64649

C 2.82551 2.18157 -1.10071

C 5.45370 1.50377 -0.34747

C 3.35128 0.91446 -1.39790

C 3.63877 3.10009 -0.42125

C 4.94371 2.76861 -0.04982

C 4.65236 0.57825 -1.02094

H 2.74375 0.17214 -1.91027

H 3.24640 4.08699 -0.18349

H 5.55867 3.49895 0.47053

H 5.03059 -0.41530 -1.24341

H 6.46627 1.23874 -0.05472

C -3.72324 -1.86113 1.20903

C -5.18748 -3.59825 -0.46033

C -5.08581 -1.64353 0.96098

C -3.10403 -2.96531 0.60122

C -3.82894 -3.82481 -0.22455

C -5.81458 -2.50315 0.13563

H -5.58314 -0.79304 1.42266

H -2.04318 -3.14362 0.75477

H -3.32757 -4.66991 -0.68854

H -6.87168 -2.31729 -0.03731

H -5.75051 -4.26895 -1.10384

C 0.42568 0.91113 3.44644

C 2.15307 3.10382 3.87289

C -0.00476 2.03973 4.16074

C 1.74388 0.90246 2.95797

C 2.59792 1.98586 3.16238

C 0.85099 3.12360 4.37379

H -1.01085 2.07842 4.56774

H 2.10304 0.03800 2.40385

H 3.60627 1.95569 2.76017

H 0.49604 3.98333 4.93652

H 2.81694 3.94792 4.03905

H 0.36197 -2.83655 -4.20894

H -2.07251 2.09159 2.10856

H -2.75782 1.53838 0.57659

C 3.01199 -2.94445 -0.85249

C 4.18943 -3.56032 -1.32070

C 5.25689 -3.83695 -0.46688

C 5.17614 -3.52178 0.89188

C 4.00825 -2.93516 1.38216

C 2.94351 -2.65735 0.52416

H 4.25333 -3.84909 -2.36545

H 6.14899 -4.31744 -0.86223

H 6.00476 -3.74365 1.55963

H 3.92458 -2.69229 2.43938

H 2.04062 -2.19857 0.91690

C 1.87544 -2.62936 -1.76994

C 0.50401 -2.62117 -1.19526

H -0.24731 -2.81545 -1.97203

H 0.39389 -3.39731 -0.42605

C 2.14363 -2.33188 -3.06905

H 3.17832 -2.27051 -3.39882

C 1.09111 -2.01983 -4.09743


H 1.53551 -1.83766 -5.08214

H 0.50222 -1.12617 -3.82930

(R,S)-TS4-cis Charge: 0

Multiplicity: 1





2930.358773


Geometry:

C -2.13672 -1.56366 2.82431

C -3.38693 -1.03327 2.46022

C -4.19201 -0.38535 3.39865

C -3.76929 -0.25394 4.72355

C -2.53252 -0.77977 5.10185

C -1.72693 -1.42479 4.16219

H -3.72117 -1.12410 1.43290

H -5.15579 0.01562 3.09364

H -4.39992 0.24644 5.45390

H -2.19651 -0.69632 6.13264

H -0.77561 -1.85001 4.46966

C -1.25130 -2.25662 1.83804

C 0.08952 -1.82997 1.77215

H 0.82543 -2.50858 1.34254

H 0.46079 -1.21588 2.59073

C -1.78159 -3.22564 0.95245

H -1.00699 -3.78686 0.42648

C -2.99979 -4.06378 1.27059

H -2.72779 -4.93659 1.88547

H -3.47219 -4.45376 0.36155

Cu 0.11412 -0.33178 0.20308

H -3.76425 -3.50912 1.82025

C -6.10064 -2.62625 -2.17023

C -5.13021 -3.61579 -2.34773

C -3.81664 -3.38839 -1.93861

C -3.44932 -2.17065 -1.34112

C -4.42907 -1.17335 -1.18774

C -5.74197 -1.40387 -1.59236

H -7.12461 -2.80138 -2.48967

H -5.39653 -4.56348 -2.80915

H -3.06074 -4.15648 -2.08967

H -4.13193 -0.21560 -0.77156

H -6.48919 -0.62331 -1.46965

C -2.04395 -1.91891 -0.94701

O -1.65590 -0.73142 -0.68695

H -1.31904 -2.62785 -1.37902

P 0.77415 1.82059 0.79106

C 1.78408 1.95626 2.41652

C 1.46608 3.35430 2.98720

C 0.00303 3.66118 2.65664

C -0.18391 3.43166 1.13755

H 1.66480 3.38778 4.06555

H 2.10178 4.11749 2.52172

H -0.27651 4.68685 2.92561


H -0.66153 2.99102 3.21721

P 1.75851 -0.35397 -1.49515

C 1.06358 -0.19873 -3.26911

C 2.14336 -0.80397 -4.18649

C 2.73066 -2.01456 -3.45512

C 3.15135 -1.54788 -2.04011

H 1.72269 -1.07485 -5.16296

H 2.94577 -0.07947 -4.37453

H 3.58764 -2.44585 -3.98636

H 1.97365 -2.80569 -3.37867

H 1.29442 1.21689 3.06244

H 0.36725 4.22462 0.61401

C 2.74458 1.21720 -1.20451

H 3.21552 1.55855 -2.13498

H 3.54948 0.92889 -0.51830

C 1.92357 2.36532 -0.58735

H 0.21118 -0.88976 -3.25326

H 4.04967 -0.92641 -2.14862

C 0.52629 1.17336 -3.61929

C -0.53725 3.72529 -4.18454

C -0.75864 1.53484 -3.17508

C 1.26338 2.11366 -4.35478

C 0.73585 3.37710 -4.63623

C -1.28278 2.79749 -3.45156

H -1.33768 0.82410 -2.58996

H 2.25271 1.86528 -4.72707

H 1.32302 4.08612 -5.21476

H -2.27259 3.05624 -3.08673

H -0.94730 4.70729 -4.40582

C 3.46935 -2.66852 -1.07513

C 4.11979 -4.78229 0.67781

C 2.52307 -3.65414 -0.75094

C 4.74446 -2.76348 -0.50044

C 5.06979 -3.80901 0.36725

C 2.84343 -4.69963 0.11483

H 1.52195 -3.59919 -1.17100

H 5.49289 -2.01085 -0.73873

H 6.06816 -3.86407 0.79411

H 2.09349 -5.44949 0.35239

H 4.36914 -5.59793 1.35105

C -1.62496 3.47547 0.67762

C -4.32620 3.66914 -0.10251

C -2.06779 4.53287 -0.12953

C -2.55910 2.51016 1.08397

C -3.89598 2.60865 0.69919

C -3.40576 4.63231 -0.51794

H -1.35693 5.29004 -0.45390

H -2.24390 1.66636 1.69139

H -4.60112 1.85078 1.02929

H -3.72686 5.46395 -1.14021

H -5.36886 3.74325 -0.40022

C 3.24335 1.56977 2.30796

C 5.94054 0.75719 2.07208

C 4.25359 2.49453 1.99742

C 3.61894 0.22989 2.50566

C 4.94859 -0.17465 2.38675

C 5.58650 2.09358 1.88132


H 4.00880 3.54251 1.85227

H 2.85659 -0.50477 2.75184

H 5.20559 -1.21911 2.53906

H 6.34918 2.83152 1.64563

H 6.97840 0.44694 1.98491

H 2.59701 3.16159 -0.24727

H 1.26372 2.79815 -1.34820

(R,R)-TS4-cis Charge: 0

Multiplicity: 1





2930.358754


Geometry:

C 1.45161 3.73579 -1.11082

C 1.41546 4.32123 0.16672

C 2.48926 5.07224 0.64897

C 3.62259 5.26729 -0.14275

C 3.67340 4.69721 -1.41696

C 2.60469 3.93313 -1.88968

H 0.53401 4.18684 0.78641

H 2.43761 5.50944 1.64315

H 4.45548 5.85899 0.22763

H 4.54464 4.85319 -2.04888

H 2.64660 3.49951 -2.88492

C 0.30234 2.95207 -1.66937

C 0.55707 1.60991 -2.08562

H -0.09012 1.22767 -2.87769

H 1.60726 1.34461 -2.21855

C -0.96469 3.53904 -1.74257

H -1.70136 2.96333 -2.30184

C -1.22709 5.02498 -1.71184

H -1.24308 5.43905 -2.73216

H -2.20289 5.25780 -1.26880

P -0.40762 -1.98526 -1.10594

C 0.69395 -2.45848 -2.60738

C -0.18511 -3.34425 -3.52560

C -1.65830 -2.99876 -3.26993

C -1.85261 -3.03746 -1.73647

H 0.09764 -3.20427 -4.57585

H -0.03162 -4.40519 -3.29683

H -2.33596 -3.70370 -3.76642

H -1.89904 -1.99760 -3.65264

P 1.08378 -0.48194 1.40893

C -0.02391 -0.07425 2.92230

C 0.93473 0.43147 4.03067

C 2.21444 0.97098 3.37292

C 2.67565 -0.11220 2.37451

H 0.43763 1.18993 4.64728

H 1.20933 -0.38848 4.70404

H 2.99657 1.17752 4.11334

H 2.01458 1.91224 2.84395

H 0.83355 -1.49347 -3.10689


H -1.62691 -4.06675 -1.42043

Cu 0.02136 0.30244 -0.51384

C 1.23013 -2.34026 1.22887

H 1.27333 -2.82102 2.21343

H 2.20674 -2.48541 0.75000

C 0.13059 -2.99562 0.37678

H -0.60226 0.77927 2.55448

H 2.87238 -1.02123 2.96075

C -1.01217 -1.15837 3.29671

C -2.89464 -3.18513 3.86623

C -2.29304 -1.14137 2.71727

C -0.69574 -2.21379 4.16697

C -1.62796 -3.21420 4.45187

C -3.22264 -2.14440 2.99404

H -2.55085 -0.34205 2.02705

H 0.28363 -2.26160 4.63531

H -1.36054 -4.01746 5.13399

H -4.19987 -2.11242 2.52026

H -3.61854 -3.96495 4.08732

C 3.91926 0.18495 1.56927

C 6.29215 0.70059 0.13592

C 3.99526 1.26259 0.67310

C 5.05184 -0.62814 1.72867

C 6.22913 -0.37543 1.02246

C 5.17061 1.51636 -0.03530

H 3.13402 1.90580 0.52120

H 5.01151 -1.46770 2.41962

H 7.09453 -1.01698 1.16878

H 5.20337 2.35843 -0.71982

H 7.20732 0.90540 -0.41380

C -3.25111 -2.71143 -1.25110

C -5.90173 -2.22734 -0.41910

C -4.17373 -3.76260 -1.12260

C -3.67791 -1.41056 -0.94796

C -4.99207 -1.17449 -0.53353

C -5.48682 -3.52739 -0.71575

H -3.85602 -4.77971 -1.34483

H -2.98071 -0.57911 -0.99682

H -5.29800 -0.16047 -0.29074

H -6.18146 -4.35869 -0.62459

H -6.92224 -2.03776 -0.09632

C 2.06820 -2.98553 -2.25425

C 4.65109 -3.86911 -1.52360

C 2.31630 -4.33810 -1.96914

C 3.14612 -2.08834 -2.16683

C 4.42151 -2.51983 -1.80154

C 3.59354 -4.77571 -1.61188

H 1.51159 -5.06550 -2.02934

H 2.97736 -1.03549 -2.37990

H 5.23057 -1.79894 -1.72799

H 3.75974 -5.82949 -1.40249

H 5.64385 -4.21059 -1.24311

H -0.46415 5.57639 -1.15556

H 0.44359 -4.00259 0.07669

H -0.78407 -3.10103 0.97337

C -5.83947 4.25351 -0.29131

C -4.89323 4.83574 0.55416


C -3.62788 4.26248 0.68822

C -3.29134 3.09320 -0.01337

C -4.25276 2.51434 -0.86143

C -5.51117 3.09237 -1.00152

H -6.82440 4.69986 -0.39904

H -5.13969 5.73677 1.10999

H -2.89356 4.71668 1.35017

H -3.99272 1.61684 -1.41291

H -6.24167 2.63915 -1.66716

C -1.96105 2.47721 0.17426

O -1.76232 1.24638 -0.03700

H -1.28662 3.02444 0.85050

(S,R)-TS4-cis Charge: 0

Multiplicity: 1





2930.362463


Geometry:

C -0.34687 3.52713 -1.56252

C 0.62081 4.25142 -2.27852

C 1.12008 5.46154 -1.79156

C 0.67339 5.96368 -0.56735

C -0.28303 5.24986 0.15848

C -0.79282 4.04822 -0.33664

H 0.96598 3.86816 -3.23499

H 1.85390 6.01501 -2.37288

H 1.06272 6.90382 -0.18536

H -0.63873 5.63236 1.11224

H -1.53839 3.50007 0.22778

C -0.88245 2.24718 -2.12390

C 0.04374 1.21288 -2.36366

H -0.24160 0.43739 -3.07622

H 1.10122 1.47385 -2.37344

C -2.27538 2.09122 -2.31827

H -2.52491 1.23983 -2.95398

C -3.21014 3.26739 -2.50155

H -3.10180 3.71526 -3.50222

H -4.25667 2.96040 -2.40228

P 0.46336 -2.23654 -0.92196

C 1.77618 -2.72951 -2.21994

C 1.47166 -4.20003 -2.55800

C -0.05072 -4.32854 -2.65210

C -0.66643 -3.71905 -1.36690

H 1.97023 -4.50418 -3.48694

H 1.84004 -4.86300 -1.76512

H -0.37339 -5.36956 -2.77272

H -0.41169 -3.78193 -3.53210

P 1.27159 -0.06238 1.43760

C 0.10964 0.08180 2.95363

C 0.90682 0.85491 4.02907

C 1.88220 1.79676 3.31214

C 2.65029 0.93997 2.27971


H 0.22558 1.39587 4.69733

H 1.48350 0.16498 4.65687

H 2.57940 2.27739 4.00906

H 1.33520 2.59883 2.79930

H 1.50061 -2.12336 -3.09389

H -0.52629 -4.43992 -0.55175

Cu -0.01052 0.02826 -0.55509

C 2.01908 -1.78104 1.45418

H 2.20538 -2.11921 2.48067

H 2.99394 -1.67178 0.96426

C 1.17270 -2.83205 0.71241

H -0.67559 0.73954 2.56691

H 3.24635 0.20949 2.84451

C -0.55639 -1.20923 3.38131

C -1.85483 -3.61966 4.07866

C -1.79916 -1.55095 2.81901

C 0.01955 -2.10045 4.30094

C -0.62264 -3.29216 4.64658

C -2.44020 -2.74181 3.16252

H -2.24803 -0.87586 2.09553

H 0.97419 -1.86739 4.76433

H -0.15845 -3.96222 5.36608

H -3.40115 -2.97890 2.71340

H -2.35599 -4.54434 4.35302

C 3.58760 1.70890 1.37627

C 5.39038 3.18390 -0.21244

C 3.11839 2.63681 0.43274

C 4.97323 1.53324 1.50409

C 5.86942 2.26317 0.72089

C 4.01176 3.36592 -0.35317

H 2.05027 2.78957 0.30420

H 5.35502 0.81930 2.23096

H 6.93932 2.11353 0.84352

H 3.62154 4.07946 -1.07275

H 6.08369 3.75760 -0.82222

C -2.14492 -3.41420 -1.47282

C -4.91837 -2.94487 -1.69874

C -3.05161 -3.99940 -0.57789

C -2.65537 -2.58011 -2.48002

C -4.02660 -2.35101 -2.59573

C -4.42452 -3.76722 -0.68578

H -2.67726 -4.64775 0.21116

H -1.97603 -2.10001 -3.18009

H -4.39840 -1.70719 -3.38877

H -5.10729 -4.23586 0.01831

H -5.98640 -2.76704 -1.78931

C 3.19887 -2.37272 -1.84676

C 5.81759 -1.60373 -1.12656

C 4.10872 -3.30913 -1.33387

C 3.63379 -1.04510 -2.00174

C 4.92387 -0.66035 -1.64075

C 5.40644 -2.92845 -0.98001

H 3.81683 -4.34816 -1.21620

H 2.94424 -0.30502 -2.40037

H 5.22629 0.37677 -1.75112

H 6.09543 -3.67403 -0.59096

H 6.82481 -1.30759 -0.84645


H -3.03687 4.06232 -1.77091

H 1.75729 -3.75030 0.57194

H 0.29914 -3.09298 1.32148

C -6.20291 2.92868 1.19512

C -6.35256 2.15432 0.04165

C -5.25355 1.49162 -0.50307

C -3.98322 1.59202 0.08950

C -3.85060 2.35638 1.26118

C -4.94730 3.02288 1.80356

H -7.05830 3.44582 1.62185

H -7.32771 2.06356 -0.43055

H -5.37543 0.87755 -1.39284

H -2.88066 2.40046 1.74656

H -4.82731 3.61099 2.71034

C -2.83637 0.84286 -0.48079

O -1.78856 0.64124 0.22588

H -3.12211 0.07931 -1.21474

(S,S)-TS4-cis Charge: 0

Multiplicity: 1





2930.362479


Geometry:

C 1.50500 0.58558 -3.49403

C 2.62392 1.37451 -3.17153

C 2.83232 2.61983 -3.76771

C 1.92799 3.10777 -4.71336

C 0.81703 2.33408 -5.05672

C 0.60954 1.09272 -4.45348

H 3.33623 1.00766 -2.43921

H 3.70386 3.20864 -3.49212

H 2.09122 4.07470 -5.18203

H 0.11235 2.69349 -5.80275

H -0.24799 0.49182 -4.74221

C 1.24496 -0.73808 -2.84277

C -0.06320 -0.95803 -2.32957

H -0.38229 -1.99317 -2.22012

H -0.85044 -0.30210 -2.69952

C 2.27071 -1.68212 -2.68860

H 1.93500 -2.65018 -2.31914

C 3.52217 -1.74614 -3.53038

H 3.40106 -2.47547 -4.34640

H 4.39324 -2.07938 -2.95129

Cu -0.04861 -0.34750 -0.28993

H 3.77165 -0.78796 -3.99409

C 5.66862 -4.42142 0.10882

C 6.07641 -3.16116 -0.33298

C 5.13833 -2.14223 -0.50215

C 3.77785 -2.36589 -0.23091

C 3.38036 -3.63631 0.22397

C 4.31599 -4.65309 0.38670

H 6.39766 -5.21648 0.24113


H 7.12579 -2.97031 -0.54311

H 5.46028 -1.15777 -0.83505

H 2.33115 -3.80208 0.44800

H 3.99528 -5.63144 0.73652

C 2.79731 -1.27112 -0.37527

O 1.67043 -1.32493 0.19913

H 3.21968 -0.29413 -0.64897

P -0.65578 1.84438 0.24335

C -1.68434 2.71060 -1.12707

C -1.30279 4.20658 -1.06270

C 0.15790 4.29861 -0.60955

C 0.28100 3.44796 0.67624

H -1.46497 4.68604 -2.03568

H -1.93068 4.73768 -0.33702

H 0.46419 5.33370 -0.41546

H 0.82387 3.90562 -1.38850

P -1.61862 -1.14132 1.29064

C -0.92251 -1.84870 2.92031

C -2.03954 -2.74520 3.48485

C -2.65531 -3.48859 2.29608

C -3.02485 -2.43692 1.21914

H -1.64895 -3.43307 4.24542

H -2.81664 -2.13978 3.96923

H -3.53996 -4.07060 2.58132

H -1.92672 -4.19922 1.88550

H -1.24789 2.29803 -2.04400

H -0.32292 3.93929 1.45144

C -2.59132 0.38492 1.79177

H -3.03087 0.25904 2.78934

H -3.42076 0.44804 1.07769

C -1.77061 1.68699 1.74536

H -0.11232 -2.50051 2.56875

H -3.92685 -1.91256 1.56001

C -0.30834 -0.81779 3.84261

C 0.89914 1.13454 5.48310

C 0.99279 -0.35487 3.57626

C -0.98811 -0.28680 4.94883

C -0.38933 0.67910 5.76276

C 1.58832 0.61267 4.38463

H 1.52904 -0.74902 2.71636

H -1.98761 -0.63310 5.19402

H -0.93308 1.06985 6.61940

H 2.58941 0.96311 4.15102

H 1.36477 1.88499 6.11656

C -3.30809 -3.02001 -0.14785

C -3.88968 -4.16110 -2.66088

C -2.32908 -3.73124 -0.86011

C -4.58016 -2.88934 -0.72204

C -4.87129 -3.45356 -1.96657

C -2.61599 -4.29686 -2.10209

H -1.32864 -3.83207 -0.44652

H -5.35287 -2.34276 -0.18563

H -5.86719 -3.34378 -2.38868

H -1.84178 -4.84115 -2.63642

H -4.11244 -4.60234 -3.62861

C 1.68709 3.29470 1.20918

C 4.32207 3.11722 2.19775


C 2.03340 3.86010 2.44421

C 2.68589 2.63390 0.47760

C 3.98895 2.54581 0.96647

C 3.33801 3.77595 2.93587

H 1.27285 4.37590 3.02646

H 2.43787 2.18448 -0.47935

H 4.74763 2.02760 0.38537

H 3.58347 4.22721 3.89396

H 5.33880 3.04993 2.57561

C -3.16102 2.37640 -1.13091

C -5.89300 1.64396 -1.14005

C -4.10859 3.10158 -0.39005

C -3.61874 1.28067 -1.88257

C -4.96474 0.91406 -1.88612

C -5.45800 2.74127 -0.39530

H -3.80079 3.96351 0.19435

H -2.90724 0.70543 -2.46889

H -5.28378 0.05699 -2.47287

H -6.17020 3.32454 0.18299

H -6.94355 1.36591 -1.14506

H -2.44279 2.54998 1.82505

H -1.08841 1.72530 2.60307

(R,S)-TS4-trans Charge: 0

Multiplicity: 1





2930.367314


Geometry:

P 0.02846 -2.06334 -1.10793

C 1.19305 -2.45901 -2.57929

C 0.62749 -3.73345 -3.23803

C -0.89794 -3.65403 -3.15038

C -1.25813 -3.37012 -1.67423

H 0.98099 -3.82540 -4.27250

H 0.96712 -4.62995 -2.70484

H -1.38229 -4.57705 -3.49116

H -1.26988 -2.84406 -3.79097

P 1.29015 -0.34494 1.44358

C 0.11649 -0.22068 2.95991

C 0.97909 0.29129 4.13916

C 2.15345 1.09805 3.57307

C 2.79592 0.22096 2.47976

H 0.36590 0.88333 4.82899

H 1.37993 -0.54922 4.71714

H 2.88725 1.35327 4.34707

H 1.79255 2.04336 3.14764

H 0.99935 -1.62073 -3.26037

H -1.01104 -4.27220 -1.09918

Cu 0.06248 0.27435 -0.48899

C 1.74165 -2.14995 1.20556

H 1.89394 -2.63744 2.17608

H 2.71380 -2.12718 0.69683


C 0.73676 -2.96546 0.37574

H -0.56037 0.58222 2.65225

H 3.14588 -0.69728 2.97192

C -0.73458 -1.44375 3.23023

C -2.37825 -3.69952 3.66092

C -2.02180 -1.51788 2.67032

C -0.28869 -2.52528 4.00757

C -1.10125 -3.64083 4.22142

C -2.83422 -2.63241 2.88316

H -2.37405 -0.69785 2.04989

H 0.69788 -2.50285 4.46215

H -0.73506 -4.46204 4.83270

H -3.82284 -2.66499 2.43441

H -3.01248 -4.56532 3.83301

C 3.97359 0.81155 1.74209

C 6.23294 1.87618 0.42505

C 3.97846 2.13416 1.27336

C 5.12588 0.03705 1.53919

C 6.24473 0.56032 0.88938

C 5.09341 2.66003 0.61994

H 3.10640 2.76151 1.42802

H 5.14901 -0.98815 1.90191

H 7.12706 -0.05982 0.75345

H 5.07277 3.68588 0.26204

H 7.10321 2.29002 -0.07721

C -2.71782 -3.05680 -1.43549

C -5.47123 -2.57701 -1.05304

C -3.48539 -3.88271 -0.60201

C -3.35682 -1.98238 -2.07207

C -4.71788 -1.74322 -1.88390

C -4.84911 -3.64856 -0.41127

H -3.01013 -4.72237 -0.09971

H -2.78530 -1.31989 -2.71535

H -5.18852 -0.90166 -2.38483

H -5.42421 -4.30816 0.23380

H -6.53275 -2.39338 -0.91001

C 2.67297 -2.45083 -2.26566

C 5.43517 -2.34743 -1.68558

C 3.36788 -3.59862 -1.85222

C 3.39565 -1.25175 -2.38604

C 4.75835 -1.19663 -2.09611

C 4.73449 -3.54813 -1.56706

H 2.84903 -4.54818 -1.76100

H 2.87755 -0.35185 -2.70804

H 5.28927 -0.25350 -2.18629

H 5.25089 -4.45319 -1.25696

H 6.49871 -2.30924 -1.46601

H -2.44986 1.71159 -3.65084

H 1.19051 -3.91872 0.07711

H -0.13700 -3.20345 0.99355

C 0.25201 4.02504 -1.44885

C -0.19068 5.30836 -1.82085

C 0.49863 6.45567 -1.42810

C 1.65246 6.35227 -0.64987

C 2.11333 5.08638 -0.28176

C 1.42620 3.93982 -0.68005

H -1.06976 5.40595 -2.45022


H 0.13611 7.43237 -1.73918

H 2.18955 7.24504 -0.34025

H 3.01096 4.99448 0.32503

H 1.79003 2.95995 -0.39030

C -0.48704 2.80247 -1.88491

C 0.23594 1.60456 -2.16034

H -0.23887 0.92784 -2.87259

H 1.30535 1.72018 -2.33690

C -1.88661 2.86459 -1.90173

H -2.35040 3.83470 -1.75656

C -2.71894 1.81873 -2.58815

H -3.78432 2.06299 -2.53391

H -2.57453 0.83974 -2.11265

C -6.21211 3.29339 0.86565

C -5.19561 4.24805 0.97262

C -3.86777 3.87912 0.76893

C -3.53374 2.55165 0.45347

C -4.55906 1.59683 0.35691

C -5.88753 1.96893 0.55795

H -7.24834 3.57939 1.02666

H -5.43998 5.27858 1.21801

H -3.07625 4.62175 0.84995

H -4.29521 0.56949 0.12718

H -6.67399 1.22183 0.48088

C -2.11149 2.16372 0.27469

O -1.77051 0.94105 0.24909

H -1.38430 2.92275 0.59886

(R,R)-TS4-trans Charge: 0

Multiplicity: 1





2930.367450


Geometry:

Cu 0.12346 -0.51163 -0.08473

H -0.31344 -4.79968 -1.43623

C -2.39239 -2.75945 1.60957

C -3.38589 -3.73126 1.82207

C -4.32255 -3.59665 2.84707

C -4.29303 -2.48236 3.68717

C -3.31230 -1.50708 3.49253

C -2.37445 -1.64671 2.47019

H -3.40868 -4.61431 1.19054

H -5.07466 -4.36831 2.99155

H -5.02392 -2.37534 4.48456

H -3.28273 -0.63010 4.13543

H -1.62848 -0.87520 2.30807

C -1.37462 -2.92559 0.52917

C -0.05122 -2.48043 0.77268

H 0.74059 -2.91988 0.16750

H 0.23245 -2.34767 1.81666

C -1.81354 -3.38969 -0.72042

H -2.81981 -3.79205 -0.77504


C -0.85235 -3.89800 -1.76702

H -1.37911 -4.15385 -2.69402

H -0.09216 -3.14575 -2.01669

C -6.60316 -1.59535 -1.71800

C -5.84106 -2.14694 -2.75114

C -4.44974 -2.06849 -2.71063

C -3.79521 -1.43751 -1.64020

C -4.57023 -0.88266 -0.60838

C -5.96077 -0.96554 -0.64719

H -7.68803 -1.65534 -1.74667

H -6.33145 -2.63446 -3.59016

H -3.85850 -2.49595 -3.51846

H -4.07043 -0.40860 0.22902

H -6.54727 -0.54122 0.16401

C -2.31240 -1.34542 -1.63847

O -1.70953 -0.43130 -0.99023

H -1.83593 -1.74772 -2.54677

P 1.94838 0.13479 -1.42163

C 1.44715 0.90981 -3.09852

C 2.60822 0.60508 -4.06642

C 3.16920 -0.77226 -3.69486

C 3.46884 -0.74468 -2.17880

H 2.26815 0.64658 -5.10851

H 3.40780 1.34863 -3.96266

H 4.07623 -1.01637 -4.26080

H 2.43118 -1.55228 -3.92259

P 0.55696 1.36670 1.32330

C 1.25998 0.84472 3.03176

C 0.67699 1.84328 4.05955

C -0.68131 2.32609 3.53683

C -0.45521 2.78580 2.07742

H 0.60044 1.37527 5.04845

H 1.33732 2.71163 4.17031

H -1.08646 3.14628 4.14156

H -1.42080 1.51430 3.56291

H 0.59244 0.29049 -3.39749

H 4.30353 -0.04736 -2.02678

C 1.88379 2.33908 0.42817

H 2.48002 2.93313 1.13110

H 1.32728 3.04280 -0.20237

C 2.81605 1.48302 -0.44557

H 0.77538 -0.12413 3.19798

H 0.23153 3.64328 2.12090

C 2.75487 0.61226 3.07053

C 5.53541 0.10558 3.06244

C 3.25738 -0.67936 2.83879

C 3.67930 1.64364 3.30393

C 5.05318 1.39346 3.30172

C 4.62953 -0.93189 2.83087

H 2.56169 -1.49548 2.65939

H 3.33132 2.65420 3.49797

H 5.74669 2.20887 3.49137

H 4.98655 -1.94029 2.64182

H 6.60472 -0.08825 3.06345

C -1.70564 3.23712 1.34972

C -4.05926 4.17203 0.11134

C -2.57488 2.34715 0.70267


C -2.03282 4.60252 1.35668

C -3.19810 5.06892 0.74762

C -3.74022 2.81256 0.08857

H -2.32997 1.29185 0.63716

H -1.36490 5.30845 1.84692

H -3.43003 6.13091 0.76736

H -4.39175 2.10437 -0.41614

H -4.96726 4.53007 -0.36708

C 3.85854 -2.06914 -1.56265

C 4.65277 -4.53189 -0.43566

C 5.06410 -2.18490 -0.85559

C 3.05780 -3.21435 -1.69410

C 3.44836 -4.43172 -1.13684

C 5.46034 -3.40250 -0.29748

H 5.70294 -1.31146 -0.74446

H 2.11771 -3.15545 -2.23413

H 2.80901 -5.30310 -1.25040

H 6.40377 -3.46749 0.23884

H 4.95781 -5.48130 -0.00405

C 0.95793 2.34001 -3.00674

C -0.02499 4.97105 -2.73468

C 1.78249 3.44631 -3.26106

C -0.37263 2.57846 -2.61822

C -0.85783 3.87862 -2.47800

C 1.29459 4.74938 -3.12954

H 2.81210 3.30240 -3.57481

H -1.02225 1.73408 -2.39965

H -1.88438 4.03475 -2.15932

H 1.95065 5.59059 -3.33944

H -0.40294 5.98454 -2.62976

H 3.39480 2.13127 -1.11523

H 3.53308 0.95047 0.19162

(S,S)-TS4-trans Charge: 0

Multiplicity: 1





2930.367316


Geometry:

P 2.20956 0.68322 -1.01515

C 1.94002 1.86016 -2.51049

C 3.27211 1.87195 -3.29305

C 3.91803 0.49334 -3.13506

C 3.95088 0.18051 -1.62131

H 3.09926 2.13253 -4.34450

H 3.95389 2.62834 -2.88654

H 4.92955 0.45895 -3.55745

H 3.32653 -0.26827 -3.66045

P 0.04857 1.07388 1.46760

C 0.46705 0.00805 3.00566

C -0.23084 0.69081 4.20028

C -1.53109 1.31422 3.68581

C -1.15886 2.17925 2.46030


H -0.40817 -0.03128 5.00651

H 0.39758 1.48683 4.61761

H -2.02783 1.92638 4.44820

H -2.23753 0.52594 3.39732

H 1.20690 1.31080 -3.11313

H 4.64687 0.89094 -1.15462

Cu 0.00067 -0.32484 -0.43834

C 1.46206 2.28774 1.24969

H 1.80428 2.64487 2.22906

H 1.01536 3.14404 0.73013

C 2.66350 1.76184 0.44541

H -0.06489 -0.92390 2.78437

H -0.53143 3.00195 2.82917

C 1.93383 -0.33424 3.16720

C 4.66463 -1.02099 3.36658

C 2.44601 -1.46244 2.50206

C 2.81727 0.43854 3.93699

C 4.16885 0.09746 4.03747

C 3.79610 -1.79992 2.59733

H 1.77501 -2.06223 1.89243

H 2.45802 1.31146 4.47428

H 4.83179 0.70800 4.64579

H 4.16992 -2.66860 2.06305

H 5.71586 -1.28574 3.44452

C -2.32854 2.79724 1.73015

C -4.55790 4.03639 0.52012

C -3.42149 2.03668 1.28556

C -2.37181 4.18689 1.54192

C -3.47052 4.80318 0.94009

C -4.52738 2.65100 0.69707

H -3.41700 0.95677 1.40190

H -1.53664 4.79525 1.88193

H -3.48023 5.88275 0.81288

H -5.36992 2.04211 0.38304

H -5.42229 4.51165 0.06424

C 4.41388 -1.21945 -1.28590

C 5.36245 -3.81900 -0.74527

C 5.65743 -1.41902 -0.67029

C 3.65192 -2.34775 -1.62391

C 4.11889 -3.63406 -1.35592

C 6.13122 -2.70536 -0.40310

H 6.26337 -0.55676 -0.40018

H 2.67981 -2.21802 -2.09022

H 3.50781 -4.49250 -1.62186

H 7.10070 -2.83526 0.07127

H 5.72742 -4.82167 -0.53906

C 1.33337 3.20694 -2.17918

C 0.11988 5.67434 -1.52464

C 2.10861 4.32464 -1.82974

C -0.06363 3.35812 -2.19871

C -0.66595 4.57305 -1.87209

C 1.50933 5.54458 -1.50770

H 3.19228 4.25465 -1.81404

H -0.68451 2.50718 -2.46748

H -1.74883 4.65651 -1.88657

H 2.13356 6.39570 -1.24717

H -0.34540 6.62440 -1.27598


H 0.19700 -3.60802 -3.41373

H 3.29477 2.60386 0.13563

H 3.27634 1.11426 1.08324

C -3.22723 -1.62108 -2.17691

C -4.17325 -2.53752 -2.67300

C -5.52391 -2.20682 -2.77718

C -5.96888 -0.93929 -2.40105

C -5.04475 -0.01264 -1.91376

C -3.69753 -0.35028 -1.79563

H -3.84163 -3.51107 -3.01894

H -6.22606 -2.93777 -3.17075

H -7.01909 -0.67412 -2.49269

H -5.37171 0.98325 -1.62809

H -2.99756 0.37643 -1.39536

C -1.77269 -1.95919 -2.15750

C -0.81530 -0.90808 -2.30739

H 0.13597 -1.21443 -2.74501

H -1.19061 0.01493 -2.75128

C -1.38572 -3.28745 -1.95657

H -2.16842 -4.03738 -1.89908

C -0.01715 -3.79077 -2.34917

H 0.06771 -4.87027 -2.17848

H 0.77425 -3.30007 -1.76911

C -4.81467 -3.43036 2.13114

C -4.22737 -4.56999 1.57280

C -2.97414 -4.48521 0.97089

C -2.28592 -3.26258 0.91344

C -2.88006 -2.12703 1.48448

C -4.13571 -2.20980 2.08409

H -5.79199 -3.49461 2.60211

H -4.74661 -5.52429 1.61129

H -2.51625 -5.37359 0.53967

H -2.33902 -1.18723 1.44602

H -4.58836 -1.32190 2.51967

C -0.93034 -3.20164 0.31237

O -0.15576 -2.21384 0.47162

H -0.48333 -4.18714 0.11196

(S,R)-TS4-trans Charge: 0

Multiplicity: 1





2930.372190


Geometry:

Cu 0.12307 -0.46790 0.12110

H -0.83448 -4.56094 -0.81903

C -2.14772 -2.38123 2.52241

C -3.22125 -3.18576 2.94789

C -3.88327 -2.93865 4.15088

C -3.48913 -1.87946 4.97008

C -2.41842 -1.07572 4.57257

C -1.75895 -1.32568 3.36916

H -3.52005 -4.03645 2.34355


H -4.70344 -3.58508 4.45357

H -4.00285 -1.68760 5.90839

H -2.09609 -0.24932 5.20215

H -0.93283 -0.69127 3.06452

C -1.42469 -2.66572 1.24518

C -0.03997 -2.33489 1.14622

H 0.53834 -2.91420 0.42797

H 0.48890 -2.20593 2.09099

C -2.16251 -3.15255 0.16170

H -3.19544 -3.43813 0.33062

C -1.49934 -3.71758 -1.06302

H -2.23970 -4.07189 -1.78675

H -0.88313 -2.95409 -1.56105

C -5.81575 -2.15212 -3.36650

C -6.07463 -2.01007 -1.99922

C -5.04908 -1.64887 -1.12891

C -3.74731 -1.42512 -1.60832

C -3.49929 -1.56025 -2.98395

C -4.52543 -1.92477 -3.85387

H -6.61546 -2.43276 -4.04695

H -7.07722 -2.17959 -1.61457

H -5.24831 -1.54156 -0.06443

H -2.49675 -1.36909 -3.35284

H -4.32158 -2.02708 -4.91700

C -2.67441 -1.01013 -0.67417

O -1.55737 -0.59081 -1.09880

H -3.01637 -0.71944 0.32689

P 1.76870 0.05158 -1.51517

C 1.06378 0.60595 -3.20551

C 2.11827 0.19828 -4.25392

C 2.74209 -1.12018 -3.78757

C 3.19974 -0.92093 -2.32253

H 1.66544 0.11284 -5.24962

H 2.90822 0.95596 -4.32743

H 3.58772 -1.42565 -4.41548

H 1.99841 -1.92584 -3.83912

P 0.65658 1.52379 1.23083

C 1.64711 1.36955 2.86422

C 1.31167 2.63799 3.67367

C -0.16531 2.95603 3.42499

C -0.37944 2.99083 1.89321

H 1.53308 2.49320 4.73842

H 1.91737 3.48721 3.33390

H -0.46539 3.91013 3.87465

H -0.79807 2.17987 3.87416

H 0.19833 -0.05783 -3.31818

H 4.05853 -0.23647 -2.33462

C 1.79783 2.44097 0.05321

H 2.42349 3.15660 0.60142

H 1.12779 3.02268 -0.59070

C 2.68537 1.53031 -0.81577

H 1.16300 0.52138 3.36509

H 0.12610 3.88837 1.51327

C 3.10843 1.01485 2.69006

C 5.80472 0.26507 2.30573

C 3.46938 -0.33200 2.51216

C 4.13038 1.97672 2.67773


C 5.46442 1.60556 2.48976

C 4.79884 -0.70479 2.31751

H 2.69426 -1.09424 2.51706

H 3.89569 3.02636 2.82619

H 6.23795 2.36944 2.49198

H 5.04473 -1.75240 2.17021

H 6.84281 -0.02216 2.16125

C -1.82771 3.05828 1.46012

C -4.53988 3.28502 0.71736

C -2.75550 2.06484 1.81085

C -2.28604 4.16327 0.72895

C -3.62818 4.27867 0.35959

C -4.09667 2.17776 1.44479

H -2.43405 1.19074 2.36975

H -1.58341 4.94470 0.44800

H -3.95975 5.14837 -0.20222

H -4.79619 1.39618 1.72930

H -5.58515 3.37122 0.43317

C 3.62146 -2.19170 -1.61841

C 4.46589 -4.57586 -0.36881

C 4.93911 -2.34036 -1.16386

C 2.73210 -3.26266 -1.43384

C 3.14882 -4.44151 -0.81620

C 5.36084 -3.52014 -0.54556

H 5.64463 -1.52343 -1.29953

H 1.70138 -3.17131 -1.76563

H 2.44121 -5.25510 -0.68077

H 6.39007 -3.61359 -0.20792

H 4.78977 -5.49540 0.11122

C 0.54927 2.02894 -3.25383

C -0.48731 4.65523 -3.27870

C 1.33550 3.11090 -3.68054

C -0.76871 2.29005 -2.83972

C -1.28085 3.58751 -2.85064

C 0.82223 4.41049 -3.69381

H 2.35466 2.94828 -4.01901

H -1.38400 1.46391 -2.49281

H -2.30096 3.76071 -2.52001

H 1.44874 5.23057 -4.03599

H -0.88721 5.66582 -3.29493

H 3.14843 2.12156 -1.61533

H 3.49653 1.11065 -0.20900

Copper alkoxide (S,R)-III Charge: 0

Multiplicity: 1





2930.391069


Geometry:

Cu -0.28765 0.12500 0.00053

H 3.74476 3.38091 1.33925

C 6.20355 0.80930 0.47153

C 6.52732 1.82917 -0.44076


C 7.72303 1.80162 -1.15814

C 8.61988 0.74453 -0.99186

C 8.30731 -0.28404 -0.10066

C 7.11443 -0.25130 0.62047

H 5.84690 2.66555 -0.57473

H 7.95456 2.60935 -1.84816

H 9.54795 0.71820 -1.55705

H 8.98888 -1.12175 0.02540

H 6.86319 -1.07025 1.28760

C 4.95026 0.86506 1.27684

C 4.97701 0.52535 2.57662

H 4.08320 0.55160 3.19410

H 5.89658 0.22734 3.07254

C 3.03864 2.54232 1.29839

H 2.13762 2.85236 0.76493

H 2.75566 2.30270 2.33139

C 4.26555 -3.27873 -1.58969

C 4.23150 -3.24791 -0.19415

C 3.69009 -2.14249 0.47048

C 3.18001 -1.04946 -0.24228

C 3.21344 -1.09763 -1.64305

C 3.75235 -2.19714 -2.31148

H 4.68696 -4.13557 -2.10973

H 4.62869 -4.08260 0.37985

H 3.67308 -2.12326 1.55773

H 2.79671 -0.26175 -2.19710

H 3.77299 -2.21212 -3.39905

C 2.59096 0.17677 0.46391

O 1.48699 0.67791 -0.21546

H 2.34531 -0.13143 1.50087

P -2.00724 0.82059 -1.42130

C -2.25132 -0.19762 -3.02421

C -2.68561 0.82544 -4.09787

C -1.99841 2.15805 -3.77524

C -2.30140 2.47654 -2.29107

H -2.43480 0.46099 -5.10139

H -3.77208 0.97379 -4.07450

H -2.34837 2.97129 -4.42191

H -0.91343 2.07493 -3.92138

P -1.80001 -0.75053 1.44435

C -1.87242 0.19543 3.10483

C -2.22618 -0.86689 4.16729

C -1.56102 -2.18209 3.73950

C -1.98443 -2.44645 2.27421

H -1.90184 -0.54207 5.16332

H -3.31113 -1.02085 4.21857

H -1.85504 -3.02173 4.38020

H -0.46824 -2.09636 3.80397

H -1.22850 -0.51317 -3.26240

H -3.37874 2.67940 -2.21477

C -3.47045 -0.55914 0.60991

H -4.26992 -0.47895 1.35607

H -3.62328 -1.49932 0.06580

C -3.54756 0.62789 -0.37183

H -0.82522 0.48084 3.26085

H -3.06353 -2.65279 2.28484

C -2.68750 1.46992 3.05878


C -4.14772 3.87643 2.83958

C -2.07920 2.64771 2.58992

C -4.04076 1.52708 3.42453

C -4.76228 2.71927 3.31922

C -2.79946 3.83628 2.47415

H -1.02970 2.62782 2.30412

H -4.54240 0.64208 3.80501

H -5.80788 2.74013 3.61593

H -2.30596 4.72679 2.09515

H -4.71114 4.80190 2.75685

C -1.29456 -3.60867 1.59232

C -0.05655 -5.82681 0.37230

C 0.05413 -3.55665 1.20699

C -2.00901 -4.79210 1.35521

C -1.39738 -5.89461 0.75480

C 0.66669 -4.65313 0.59904

H 0.63045 -2.64833 1.36077

H -3.05594 -4.85101 1.64612

H -1.96973 -6.80361 0.58675

H 1.70644 -4.57732 0.29422

H 0.42139 -6.68039 -0.10119

C -1.55482 3.66806 -1.72734

C -0.21587 5.95707 -0.77490

C -2.24386 4.87155 -1.51692

C -0.17944 3.62471 -1.44372

C 0.48012 4.76231 -0.97458

C -1.58405 6.00847 -1.04591

H -3.31019 4.91953 -1.72924

H 0.38111 2.69941 -1.55444

H 1.54271 4.70787 -0.75568

H -2.13888 6.93103 -0.89427

H 0.30372 6.83848 -0.40829

C -3.08643 -1.44881 -2.86344

C -4.57388 -3.81734 -2.46863

C -4.48149 -1.45979 -3.02045

C -2.45395 -2.65261 -2.50832

C -3.18617 -3.82301 -2.30811

C -5.21675 -2.63190 -2.82834

H -5.00665 -0.55213 -3.30365

H -1.37366 -2.66971 -2.38314

H -2.66923 -4.73482 -2.02333

H -6.29528 -2.61585 -2.96360

H -5.14748 -4.72825 -2.32000

H -4.44796 0.53848 -0.99072

H -3.62646 1.56764 0.18823

C 3.66129 1.32406 0.59672

H 3.89284 1.61146 -0.43555

Reductive coupling product (S,R)-V Charge: 0

Multiplicity: 1





2930.391069



Geometry:

C 3.02951 -0.56781 0.21408

C 2.85539 -0.31793 -1.15901

C 3.95492 -0.20298 -2.00975

C 5.25190 -0.34653 -1.51200

C 5.43980 -0.60391 -0.15255

C 4.34096 -0.71465 0.69914

H 1.85191 -0.17996 -1.54913

H 3.79744 0.00308 -3.06561

H 6.10705 -0.26414 -2.17768

H 6.44375 -0.72946 0.24519

H 4.49237 -0.93937 1.75122

C 1.86442 -0.66604 1.13693

C 1.90580 -0.09191 2.34845

H 1.07818 -0.16127 3.04920

H 2.75833 0.49842 2.67081

C 0.64147 -1.47039 0.67788

H 0.83680 -1.84202 -0.33463

C 0.42524 -2.69546 1.58626

H 1.34241 -3.29107 1.63949

H -0.37806 -3.33561 1.20864

H 0.16765 -2.39439 2.60854

C -4.10849 -2.78897 -0.75771

C -4.02242 -2.34836 0.56322

C -2.90257 -1.63008 0.98981

C -1.85384 -1.34583 0.10808

C -1.95174 -1.79025 -1.21910

C -3.06931 -2.50584 -1.64898

H -4.97941 -3.34576 -1.09321

H -4.82838 -2.55693 1.26199

H -2.84520 -1.28151 2.01856

H -1.15115 -1.56230 -1.91745

H -3.13029 -2.84357 -2.68051

C -0.62730 -0.58445 0.58245

O -0.33035 0.48593 -0.32725

H -0.83296 -0.16758 1.57573

Si -0.84026 2.05451 -0.16525

C 0.28068 3.06987 -1.26125

H 0.16453 2.80081 -2.31760

H 0.06828 4.14072 -1.16512

H 1.32802 2.90153 -0.98969

O -2.43851 2.27351 -0.55087

O -0.73437 2.44230 1.43683

C -3.03638 1.95528 -1.79777

H -4.07640 2.29541 -1.77235

H -2.53030 2.45983 -2.63310

H -3.02550 0.87343 -1.97714

C -1.42743 3.50834 2.06831

H -2.49940 3.47941 1.84240

H -1.28709 3.40958 3.14944

H -1.02688 4.48295 1.75683


IX. References

(1) Prudent Practices in the Laboratory: Handling and Management of chemical

Hazards/Committee on Prudent Practices in the Laboratory: An Update. Board on

Chemical Sciences and Technology, Division of Earth and Life Studies, National

Research Council of the National Academies. Washington, D.C.: National Academies

Press, 2011.

(2) Fiorito, D.; Folliet, S.; Liu, Y.; Mazet, C. A General Nickel-Catalyzed Kumada

Vinylation for the Preparation of 2-Substituted 1,3-Dienes. ACS Catal. 2018, 8, 1392–

1398.

(3) Nguyen, K. D.; Herkommer, D.; Krische, M. J. Enantioselective Formation of All-

Carbon Quaternary Centers via C–H Functionalization of Methanol: Iridium-Catalyzed

Diene Hydrohydroxymethylation. J. Am. Chem. Soc. 2016, 138, 14210–14213.

(4) Smith, A. B.; Kim, W.-S.; Tong, R. Uniting Anion Relay Chemistry with Pd-

Mediated Cross Coupling: Design, Synthesis and Evaluation of Bifunctional Aryl and

Vinyl Silane Linchpins. Org. Lett. 2010, 12, 588–591.

(5) Neese, F. The ORCA Program System. WIREs Comput. Mol. Sci. 2012, 2, 73–78.

(6) Frisch, M. J. et al., Gaussian 03, Revision C.02. Gaussian, Inc., Wallingford CT

(2010).

(7) Legault, C. Y. CYLView, 1.0b. University of Sherbrooke, Quebec, Canada (2009).

(8) Zhao, Y.; Truhlar, D. G. The M06 suite of density functionals for main group

thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and

transition elements: two new functionals and systematic testing of four M06-class

functionals and 12 other functionals. Theor. Chem. Acc. 2008, 120, 215–241.

(9) Zhao, Y.; Truhlar, D. G. Density Functionals with Broad Applicability in Chemistry.

Acc. Chem. Res. 2008, 41, 157–167.

(10) Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. Universal Solvation Model Based on

Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk

Dielectric Constant and Atomic Surface Tensions. J. Phys. Chem. B 2009, 113, 6378–

6396.

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Compiled NMR Spectra For




Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139,

United States



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Compiled SFC, GC and HPLC Traces for




Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139,

United States



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minor diastereomer (mixture)

minor diastereomer (mixture)

（P1）

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