European Journal of

Organic Chemistry
Supporting Information

One-Carbon Homologation of α,β-Unsaturated Aldehydes:

Access to α-Tertiary β,γ-Unsaturated Aldehydes
Arnaud Delbrassinne, Boris Junior Takam Mba, Laurent Collard, and Raphaël Robiette*
1. Additional results S2
1.1. Influence of cis/trans stereochemistry on the rearrangement S2
1.2. Origin of the moderate enantioselectivity S2
1.3. Stereospecificity of the rearrangement S4
1.4. Stability of the β,γ-unsaturated aldehydes S4
1.5. Use of Yb(OTf)3 S5
1.6. One-pot version of the methodology S5
1.6. Determination of the yield via the use of an internal standard S6
1.7. Obtaining of the corresponding β,γ-unsaturated ketones S6
2. Experimental part S7
2.1. General S7
2.2. Procedures and compounds characterization S8
2.3. HPLC analysis S23
2.4. NMR spectra S27
3. Computational details S46
3.1. Methods S46
3.2. Cartesian coordinates and energies S46

S1
1. Additional results

1.1. Influence of cis/trans stereochemistry on the rearrangement

The influence of the diasteroselectivity of the starting epoxide on the outcome of the
Meinwald rearrangement reaction was investigated. To do so, we carried out the rearrangement step
using the previously developed reaction conditions with Cu(BF4)2 starting from a pure sample of
6a-trans (Scheme S1).

Scheme S1 Investigation of the rearrangement of 6a-trans.

The obtained result was identical to the rearrangement reaction carried out on a 17/83
cis/trans mixture of 6a. This suggests that the diastereoisomeric ratio of the epoxide 6a has no
impact on the Lewis acid promoted Meinwald rearrangement reaction into 7a.

1.2. Origin of the moderate enantioselectivity

Enantiomeric ratios were measured by Chiral HPLC. Unfortunately, obtained -aldehydes
were found not to be stable enough on the column to allow the determination of the e.r.
Accordingly, we decided to carry out the HPLC analysis on the corresponding primary homoallylic
alcohol 12 obtained by reduction of the aldehydes (see Scheme S2 for 12a).1 We hypothesized that
the reduction reaction should not influence the configuration of the stereogenic center obtained after
the Meinwald rearrangement. Satisfyingly, the homoallylic alcohol 12a was found to be easy to
purify, bench- and column-stable.

Scheme S2 Synthesis of primary homoallylic alcohol 12a by reduction

The impact of the rearrangement and reduction conditions on the measured e.r. of the
alcohol was investigated (Table S1).

1
Li, Y.; Han, J.; Luo, H.; An, Q.; Cao, X.-P.; Li, B. Org. Lett. 2019, 21, 6050-6053.
S2
Table S1 Influence of the reaction conditions for the Meinwald rearrangement and reduction steps
on the e.r. of the alcohol 12a

Entry Conditions 1 Conditions 2 e.r.a

1 Cu(BF4)2 (0.1 eq), 1h NaBH4 (2 eq), MeOH, RT, 3h 74/26
2 Cu(BF4)2 (0.05 eq), 1h NaBH4 (2 eq), MeOH, RT, 3h 74/26
3 Cu(BF4)2 (0.1 eq), 30 minb NaBH4 (2 eq), MeOH, RT, 3h 73/27
4 Cu(BF4)2 (0.1 eq), 4h NaBH4 (2 eq), MeOH, RT, 3h 73/27
5 Cu(BF4)2 (0.1 eq), 1h LiAlH4 (1.1 eq), Et2O, -78°C 1h, RT 1h 75/25
a
Determined by Chiral HPLC b These conditions lead to only a partial conversion of 6a-trans. The reduction
was pursued on this mixture and the epoxide was removed by flash chromatography after the reduction step.

The trans epoxide 6a-trans was found to have an enantiomeric ratio of 98/2. The measured
enantiomeric ratio of the alcohol 12a obtained using the typical reaction conditions for the
Meinwald rearrangement step was found to be 74/26, indicating a partial stereospecificity (entry 1).
Accordingly, we investigated the origin of this partial stereospecificity (entries 2-5). One hypothesis
to explain this result is the partial epimerization of the aldehyde under the reaction conditions. This
was investigated by varying the time of the reaction. It was observed that the reaction time and the
amount of Lewis acid used did not have a significant impact on the enantioselectivity (entries 1-4).
This indicates that there is no epimerization triggered by the Lewis acid occurring during the
Meinwald rearrangement under tested reaction conditions.
We also tested if the reduction reaction had an influence on the e.r. of the obtained alcohol.
The solvent used for our reduction reaction is protic, so we decided to investigate the possibility of
the epimerization of the aldehyde triggered by the solvent prior to its reduction by NaBH4 by
performing the reduction using an aprotic solvent, the diethylether (entry 5). For this protocol, the
reducing agent was LiAlH4. The enantiomeric ratio of 12a was found to be identical when the
reduction reaction is performed in dry aprotic solvent. This indicates that the origin of the partial
loss of enantioselectivity during the Meinwald rearrangement lies in the rearrangement step itself.
This partial stereospecificity was also studied with another substitution pattern (Scheme S3).
The obtained e.r. of 12i using the same sets of reaction conditions for the rearrangement and
reduction step as the one presented in Entry 1 in Table S1 was 71/29. This indicates that the loss of
stereospecificity carries over to epoxides with different substitution as well.

Scheme S3 Synthesis of the enantioenriched alcohol 12i with the determined e.r.
S3
1.3. Stereospecificity of the rearrangement
The stereospecificity of the Meinwald rearrangement was investigated using DFT methods.
The key point here is the free energy difference between diastereomeric transition states TS-mig-
Ph-trans and TS-mig-Ph-cis, which are leading to the two different enantiomers of the desired
aldehyde (Scheme S4).

Scheme S4 Computational investigation of the stereospecificity of the rearrangement (free energies

relative to 6a-trans in kcal/mol).

Our computational results provide a 0.6 kcal/mol free energy difference between the two
transition states predicting a weakly stereospecific rearrangement (72/28 ratio) which is in very
good agreement with experimental observations.

1.4. Stability of the β,γ-unsaturated aldehydes

The β,γ-unsaturated aldehydes are known to be poorly bench-stable at room temperature. We
investigated the stability of our β,γ-unsaturated aldehydes by leaving a sample of 7a under argon
atmosphere at room temperature for a week-end. The 1H NMR spectrum recorded after three days
showed degradation of the aldehyde. Some isomerization into the α,β-unsaturated aldehyde 8a was
observed as well (Scheme S5).

Scheme S5: Isomerization of 7a to the corresponding α-aryl α,β-unsaturated aldehyde 8a

We also investigated the stability of 7a on flash silica by performing a silica plug with a 7/3
mixture of n-hexane/AcOEt as eluent. The 1H NMR spectrum of the resulting sample also showed
some degradation of 7a and isomerisation into 8a, which would make the purification of our
aldehydes tricky.
S4
1.5. Use of Yb(OTf)3
In some case the use of Cu(BF4)2 led to the formation of complex mixture of products and
the reaction was thus reattempted changing the nature of the Lewis acid to Yb(OTf)3. For aldehydes
7e,t, the desired product could be selectively obtained. Conversely, for 7c,k,s, complex mixtures of
products were still obtained with this Lewis acid.

1.6. One-pot version of the methodology

We have investigated the possibility of developing a one-pot version of our methodology
combining the two steps. The nature of the base, the nature and equivalence of the catalyst were
varied during this investigation (Table S2).
Table S2. Investigation of a one-pot version of the methodology

Entry Conditions 1 LA (eq) Outcome

1 LiHMDS (1.2 eq), -78°C to RT, 16h Cu(BF4)2 (0.05 eq) 6a
2 LiHMDS (1.2 eq), -78°C to RT, 16h Cu(BF4)2 (0.5 eq) 6a
3 LiHMDS (1.2 eq), -78°C to RT, 16h Yb(OTf)3 (0.2 eq) 6a
4 NaH (3 eq), RT, 24h Cu(BF4)2 (0.5 eq) 6a

The hypothesis that was suggested to explain these results is that the presence of HMDS or
THT, released during the epoxidation step was acting as a poison for the Lewis acid. We tested
these hypotheses by performing the rearrangement step on pure epoxide 6a in the presence of 1
equivalent of HMDS or THT. The desired aldehyde was not obtained, in both cases, the NMR
spectrum of the crude mixture shows only the epoxide 6a (Scheme S6)

Scheme S6. Rearrangement of 6a in presence of 1 eq of HMDS or THT

1.7. Determination of the yield via the use of an internal standard

S5
 During the exploration of the scope, some aldehydes (7c,k,s) were observed in complex
mixtures of products with both Lewis acids and could not be isolated due to the instability on silica
(see 1.4.). The low yields were measured by an internal standard (dimethylterephtalate) on the 1H
NMR spectra of the crude mixture of the rearrangement step performed using Cu(BF4)2 as the
Lewis acid.

1.8. Obtaining of the corresponding β,γ-unsaturated ketones

Preventing the formation of the β,γ-unsaturated ketone 9a (R1,4 =Ph) was a primary objective
of our optimization process for choosing the Lewis acid used. During the exploration of the scope
of our methodology, the ketone 9k (R4 = p-BrC6H4) was observed as a minor product; (10% yield as
compared to 24% for the corresponding aldehyde 7k). For R4 = p and m-CO2MeC6H4, the ketone 9l
and 9p were found to be the only rearrangement product observed. This can be accounted for by the
competition of the migration of R4 and H in the intermediate, the zwitterion 10 (Scheme S6). For
these migrating groups, the migration of the H becomes competitive and the ketone is observed.

Scheme S6: Competition between the migration of R4 and H

S6
2. Experimental part
2.1. General

Solvents: Solvents for extractions and purification by chromatography were obtained from
commercial sources and used without further purification, unless mentioned otherwise. Solvents for
reactions were dried over alumina column (MBraun SPS-5 with MB-Pure columns).
Reactants and reagents: commercially available reagents were used as purchased, unless
mentioned otherwise.
Sulfonium salts: The benzylic sulfonium salts were synthesized using the protocols reported in the
following articles:
• S. Clergue, O. Rousseau, T. Delaunay, G. Dequirrez, T. V. Tran, S. El Aakchioui, G.
Barozzino-Consiglio, R. Robiette, Chem. Eur. J. 2018, 11417-11425.
• A. Delbrassinne, M. Richald, J. Janssens, R. Robiette, Eur. J. Org. Chem. 2021, 2862-2868.
NaH dispersed in mineral oil: The %wt of the NaH in the mineral oil was determined by 1H NMR
titration with diethyl diethylephosphonacetate as titrating agent. The mineral oil was washed off
with three portions of n-hexane before use.
Lewis acids: The Lewis acids are supplied in their hydrated form (Cu(BF4)2.xH2O,
Yb(OTf)3.xH2O) and were used without drying prior to the reaction.
Temperatures: the reactions requiring a temperature higher than room temperature were carried
out using a silicon oil bath. The temperature was controlled by a temperature probe. The reactions
requiring a temperature of -78°C were carried out using an acetone/dry ice bath. The temperature of
0°C was achieved with the use of an ice bath.
Anhydrous conditions: Reactions requiring anhydrous conditions were performed in glassware
previously flame-dried by a Bunsen burner under reduced pressure and then cooled down under
argon atmosphere.
Thin layer chromatography (TLCs): TLCs were carried out on Merck Silica gel 60 F254
aluminium backed plates using UV light and potassium permanganate for revelation.
Flash chromatography: flash chromatography was performed using Merck Silica gel 60Å (40-63
µm).
Nuclear Magnetic Resonance (NMR) spectroscopy: NMR spectra were recorded on a Bruker
avance II 300 operating at 300 MHz for 1H and 75 MHz for 13C or on a Bruker Avance 500
spectrometer operating at 500 MHz for 1H and 125 MHz for 13C. Solvents are indicated case-by-
case. Chemical shifts (δ) are reported in ppm relative to the reference signal (TMS) and coupling
constants are given in Hertz (Hz). For some molecules, the 1H and 13C signals attributions required
additional analyses (COSY, HMQC, HMBC, 13C DEPT-Q). NMR multiplicities are abbreviated as
follow: s = singlet, d = doublet, t = triplet, q = quadruplet, sep = septet, m = multiplet.
Mass spectrometry: mass spectra and high-resolution mass spectra were recorded by the ASM
platform of the Université catholique de Louvain on a Thermo Orbitrap Exactive device.
Electrospray (ESI) in positive mode was used as ionization source. The mass values are given in
Dalton.

S7
IR spectrophotometry: IR spectrum were recorded with an infrared spectrophotometer
PerkinElmer Spectrum UATR Two. The wave numbers are given in cm-1.
Melting point: Melting points were recorded using a Büchi melting point B-540. Given
temperatures are in Celsius.
Chiral HPLC: HPLC experiments were carried out at room temperature on a quaternary pump
Waters 600 equipped with a Waters 996 DDA photodiodes array detector. The DAICEL
CHIRALPAK IA and IB columns used have particles size of 5 µm. The dimension of the two
columns is 4.6 mm x 250 mm.

2.2. Procedures and compounds characterization

2.2.1. Synthesis of β,γ-unsaturated aldehydes

2.2.1.1. General procedure

The benzylic sulfonium salt (1.4 eq.) is dissolved in a 9/1 mixture of MeCN/H2O (8 mL/100 mg of
α,β-unsaturated aldehyde) in a round-bottom flask at 0°C. Aldehyde (1 eq., 150 mg) and KOH (1.4
eq) are added and the reaction mixture is allowed to warm up to room temperature and stirred for
24-72h. Then, the reaction mixture is concentrated under reduced pressure and dissolved in
dichloromethane and water. The two layers are separated and the aqueous one is extracted twice
with dichloromethane. The combined organic layers are washed with brine, dried over MgSO4 and
concentrated under reduced pressure.
Epoxide (1 eq., 100 mg) and Cu(BF4)2 are dissolved in dry dichloromethane (6 mL/100mg of
epoxide). The reaction mixture is stirred at room temperature for a defined time (see below). Water
is added to stop the reaction. The two layers are separated and the aqueous one is extracted twice
with dichloromethane. The combined organic layers are washed with brine, dried over MgSO4 and
concentrated under reduced pressure.

For reaction leading to complex mixture of products, dimethylteraphtalate is added before the
concentration under reduced pressure. The yield is calculated on the 1H NMR spectra of the mixture
by comparing the integrations of the internal standard and the hydrogen of the aldehyde function.

The number of Cu(BF4)2 equivalents and the reaction time depend on the nature of the compound
and are reported in the description of each product. Unless mentioned otherwise the epoxide
loading is 100 mg.

S8
2.2.1.2. Product descriptions
(E)-2,4-Diphenylbut-3-enal (7a)

Eq of (CuBF4)2: 0.05 eq.

Time: 1h
Yield: 75% (85 mg)
Aspect: yellow oil

1H NMR (300 MHz, CDCl3):  = 9.76 (d, J = 2.1 Hz, 1H, H1), 7.48 – 7.17 (m, 10H, Harom), 6.54 –
6.49 (m, 2H, H3 and 4), 4.43 (dd, J = 5.5, 2.0 Hz, 1H, H2).
13C NMR (75 MHz, CDCl ):  = 198.3, 136.5, 135.6, 134.3, 129.2, 129.0, 128.6, 128.0, 127.8,
3
126.5, 124.5, 61.9.
HRMS (ESI) calculated for [M + H]+ (C16H15O): 223.11174, found: 223.11169.
IR (cm-1): 3031, 1722, 1690, 1596, 1494, 1453.

(E)-2,4-Diphenylbut-2-enal (8a)

1H NMR (300 MHz, CDCl3):  = 9.66 (s, 1H, H1), 7.48 – 7.12 (m, 10H, Harom), 6.87 (t, J = 7.6 Hz,
1H, H3), 3.70 (d, J = 7.6 Hz, 2H, H4).
13C NMR (75 MHz, CDCl ) δ = 193.7, 153.6, 144.3, 138.2, 132.3, 129.6, 129.0, 128.6, 128.6,
3
128.4, 127.0, 36.0.
HRMS (ESI) calculated for [M + H]+ (C16H15O): 223.11174, found: 223.11169.

(E)-1,4-diphenylbut-3-en-1-one (9a)

9a was never observed as the sole product of the rearrangement reaction during the optimization
process. The following description was made on a mixture of 7a and 9a.

S9
1H NMR (300 MHz, CDCl3):  = 8.08 – 7.94 (m, 2H, H10), 7.62 – 7.19 (m, 8H, Harom), 6.60 – 6.41
(m, 2H, H3 and 4), 3.92 (d, J = 5.7 Hz, 2H, H2).
HRMS (ESI) calculated for [M + H]+ (C16H15O): 223.11174, found: 223.11162.

(E)-2,4-diphenylbut-3-enal-1-d (7a-D)

Eq of (CuBF4)2: 0.1 eq.

Time: 1h
Yield: 80% (80 mg)
Aspect: yellow oil

1H NMR (300 MHz, CDCl3):  = 7.48 – 7.17 (m, 10H, Harom), 6.54 – 6.49 (m, 2H, H3 and 4), 4.43 (d,
J = 5.5, 1H, H2).
HRMS (ESI) calculated for [M + H]+ (C16H142HO): 224.11802, found: 224.11760.

(E)-4-(4-Bromophenyl)-2-phenylbut-3-enal (7b)

Eq of Cu(BF4)2: 0.05 eq.

Time: 1h
Yield: 76% (88 mg)
Aspect: yellow oil

1H NMR (300 MHz, CDCl3):  = 9.75 (d, J = 1.9 Hz, 1H, H1), 7.47 – 7.21 (m, 9H, Harom), 6.54 (dd,
J = 16.1, 7.0 Hz, 1H, H3), 6.41 (d, J = 16.1 Hz, 1H, H4), 4.41 (d, J = 7.0 Hz, 1H, H2).
13C NMR (75 MHz, CDCl ):  = 198.2, 135.5, 135.3, 133.3, 131.7, 129.3, 129.0, 128.0, 125.5,
3
121.7, 61.9.
HRMS (ESI) calculated for [M + H]+ (C16H14O79Br): 301.02225, found: 301.02223.
IR (cm-1): 3027, 1722, 1486, 1453, 1400.

S10
(E)-4-(4-Methylphenyl)-2-phenylbut-3-enal (7c)

The following description was made on a mixture of 7c and 9c.

Eq of Yb(OTf)3: 0.05 eq.
Time: 1h
Yield: 6% (Measured on the 1H NMR spectrum with an internal standard, dimethylterephtalate)
Aspect: yellow oil
1H NMR (300 MHz, CDCl3) δ 9.64 (d, J = 2.1 Hz, 1H, H1), 7.53 – 6.97 (m, 9H, Harom), 6.47 – 6.26
(m, 2H, H3 and 4), 4.35 – 4.25 (m, 1H, H2), 2.12 (s, 3H, H13).
13C NMR (75 MHz, CDCl ):  = 198.3, 137.4, 136.8, 134.4, 133.6, 129.4, 128.8, 128.5, 126.4,
3
123.5, 121.6, 62.1, 21.4.
HRMS (ESI) calculated for [M + H]+ (C17H17O): 237.12739, found: 237.13000.

(E)-1-phenyl-4-(p-tolyl)but-3-en-1-one (9c)

The following description was made on a mixture of 7c and 9c.

1H NMR (300 MHz, CDCl3) δ = 8.08 – 8.01 (m, 2H, H10), 7.53 – 6.97 (m, 7H, Harom), 6.60 – 6.40
(m, 2H, H3 and 4), 3.95 – 3.89 (d, J = 5.8 Hz, 2H, H2), 2.36 (s, 3H, H13).

(E)-5-Methyl-2-phenylhex-3-enal (7e)

Procedure note: the Lewis acid used for the Meinwald rearrangement was Yb(OTf)3
Eq of Yb(OTf)3): 0.05 eq.
Time: 1h
S11
Yield: 62% (83 mg)
Aspect: yellow oil

1H NMR (300 MHz, CDCl3):  = 9.60 (d, J = 2.4 Hz, 1H, H1), 7.38 – 7.15 (m, 5H, Harom), 5.67 (dd,
J = 15.6, 6.9 Hz, 1H, H3), 5.56 (dd, J = 15.7, 6.0 Hz, 1H, H4), 4.16 (dd, J = 6.9, 2.4 Hz, 1H, H2),
2.33 (m, 1H, H5), 1.03 – 0.93 (m, 6H, H10 and 11).
13C NMR (75 MHz, CDCl ) δ 199.0, 143.1, 136.3, 129.1, 128.8, 127.6, 121.8, 61.75, 31.5, 22.3,
3
22.3.
HRMS (ESI): calculated for [M + H]+ (C13H17O): 189.12739, found: 189.12744.

2-(Cyclohex-1-en-1-yl)-2-phenylacetaldehyde (7f)

Amount of starting epoxide: 68 mg

Eq of (CuBF4)2: 0.05 eq.
Time: 3h
Yield: 56% (determined by NMR)
Aspect: yellow oil
i1H NMR (300 MHz, CDCl ):  = 9.79 (d, J = 2.6 Hz, 1H, H1), 7.43 – 7.16 (m, 5H, Harom), 5.64 –
3
5.53 (m, 1H, H ), 4.07 (d, J = 2.6 Hz, 1H, H2), 2.20 – 2.01 (m, 2H, H5, 6, 7 or 8), 2.00 – 1.85 (m, 1H,
4

H5, 6, 7 or 8), 1.71 – 1.49 (m, 2H, H5, 6, 7 or 8), 1.26 (s, 1H, H5, 6, 7 or 8).
13C NMR (75 MHz, CDCl ):  = 200.0, 135.7, 134.3, 129.3, 128.8, 127.5, 126.9, 65.9, 28.3, 25.6,
3
22.9, 22.2.
HRMS (ESI): calculated for [M + H]+ (C14H17O): 201.12739, found: 201.12740.

(E)-3-Methyl-2,4-diphenylbut-3-enal (7g)

Eq of Cu(BF4)2: 0.05 eq.

Time: 1h
Yield: 68% (86 mg)
S12
Aspect: yellow oil

1H NMR (300 MHz, CDCl3):  = 9.90 (d, J = 2.3 Hz, 1H, H1), 7.46 – 7.12 (m, 10H, Harom), 6.38 (s,
1H, H4), 4.31 (d, J = 1.2 Hz, 1H, H2), 1.86 (s, 3H, H13).
13C NMR (75 MHz, CDCl ):  = 199.6, 137.3, 136.2, 1347, 129.9, 129.3, 129.1, 129.0, 128.9,
3
128.2, 128.1, 67.4, 17.9.
HRMS (ESI) calculated for [M + H]+ (C17H17O): 237.12739, found: 237.12726.
IR (cm-1): 3027, 1721, 1600, 1492, 1449.

4-Methyl-2-phenylpent-3-enal (7h)

Amount of starting epoxide: 153 mg

Eq of Cu(BF4)2: 0.05 eq.
Time: 1h
Yield: 40% (determined by NMR)
Aspect: yellow oil

1H NMR (300 MHz, CDCl3):  = 9.56 (d, J = 2.5 Hz, 1H, H1), 7.47 – 7.11 (m, 5H, Harom), 5.52 (dd,
J = 8.9, 1.1 Hz, 1H, H3), 4.43 – 4.36 (m, 1H, H2), 1.81 (s, 3H, H6 or 5), 1.68 (s, 3H, H5 or 6).
13C NMR (75 MHz, CDCl ):  = 198.4, 138.0, 136.8, 129.1, 128.5, 127.4, 118.5, 58.0, 26.1, 18.5.
3
HRMS (ESI): calculated for [M + H]+ (C12H15O): 175.11174, found: 175.11121.
IR (cm-1): 2978, 1721, 1494, 1450, 1377.

(E)-2,4,4-Triphenylbut-3-enal (7i)

Eq of Cu(BF4)2: 0.05 eq.

Time: 1h
Yield: 52% (80 mg)
Aspect: yellow oil

S13
1H NMR (300 MHz, CDCl3):  = 9.70 (d, J = 1.7 Hz, 1H, H1), 7.46 – 7.02 (m, 15H, Harom), 6.49 (d,
J = 10.1 Hz, 2H, H3), 4.43 (dd, J = 10.1, 1.5 Hz, 1H, H2).
13C NMR (75 MHz, CDCl ) δ 198.5, 146.0, 141.7, 139.2, 136.5, 129.8, 129.4, 128.8, 128.6, 128.4,
3
127.9, 127.8, 127.8, 127.6, 122.8, 59.5.
HRMS (ESI): calculated for [M + H]+ (C22H19O): 299.14034, found : 299.14293.
IR (cm-1): 3023, 1723, 1600, 1493, 1445.

(E)-2-(4-Fluorophenyl)-4-phenylbut-3-enal (7j)

Eq of Cu(BF4)2: 0.05 eq.

Time: 1h
Yield: 71% (84 mg)
Aspect: yellow oil

1H NMR (300 MHz, CDCl3):  = 9.70 (d, J = 1.9 Hz, 1H, H1), 7.42 – 7.15 (m, 7H, Harom), 7.13 –
7.01 (m, 2H, H12), 6.49 – 6.45 (m, 2H, H3,4), 4.39 (dd, J = 5.2, 2.6 Hz, 1H, H2).
13C NMR (75 MHz, CDCl ):  = 198.2, 135.5, 135.3, 134.6, 133.3, 132.5, 129.0, 128.7, 128.6,
3
128.1, 127.1, 126.5, 124.2, 61.0.
HRMS (ESI): calculated for [M + H]+ (C16H14OF): 241.10232, found: 241.10212.
IR (cm-1): 3035, 1721, 1691, 1600, 1507, 1222.

(E)-2-(4-Bromophenyl)-4-phenylbut-3-enal (7k)

The following description was made on a mixture of 7k and 9k.

Eq of Cu(BF4)2: 0.05 eq.

Time: 1h
S14
Yield: 24% (Measured on the 1H NMR spectrum with an internal standard, dimethylterephtalate)
Aspect: yellow oil
1H NMR (300 MHz, CDCl3) δ 9.72 (d, J = 1.9 Hz, 1H, H1), 7.57 – 7.10 (m, 9H, Harom), 6.56 – 6.38
(m, 2H, H3 and 4), 4.42 – 4.36 (m, 1H, H2).
HRMS (ESI) calculated for [M + H]+ (C16H14O79Br): 301.02225, found: 301.02209.

(E)-1-(4-bromophenyl)-4-phenylbut-3-en-1-one (9k)

The following description was made on a mixture of 7k and 9k.

1H NMR (300 MHz, CDCl3) δ = 7.89 – 7.83 (m, 2H, H10 or 11), 7.65 – 7.60 (m, 2H, H11 or 10), 7.57 –
7.10 (m, 5H, Harom), 6.60 – 6.45 (m, 2H, H3 and 4), 3.90 – 3.84 (dd, J = 6.3, 0.9 Hz, 2H, H2).

Methyl (E)-4-(1-oxo-4-phenylbut-2-en-2-yl)benzoate (8l)

The following description was made on a mixture of 8l and 9l.

Eq of Yb(OTf)3: 0.05 eq.
Time: 1h
Yield: 7 % (Measured on the 1H NMR spectrum with an internal standard, dimethylterephtalate)
Aspect: yellow oil

1H NMR (300 MHz, CDCl3):  = 9.63 (s, 1H, H1), 7.44 – 7.08 (m, 9H, Harom), 6.86 (t, J = 8.2 Hz,
1H, H3), 3.94 (s, 3H, H14), 3.63 – 3.57 (d, J = 7.5 Hz, 2H, H4).

Methyl (E)-4-(4-phenylbut-3-enoyl)benzoate (9l)

S15
 The following description was made on a mixture of 8l and 9l.
1H NMR (300 MHz, CDCl3) δ = 8.18 – 7.85 (m, 4H, H10 and 11), 7.44 – 7.08 (m, 5H, Harom), 6.54 –
6.48 (m, 2H, H3 and 4), 3.91 (s, 3H, H14), 3.90 (d, J = 5.0 Hz, 2H, H2).

(E)-4-Phenyl-2-(p-tolyl)but-3-enal (7m)

Amount of starting epoxide: 140.1 mg

Eq of Cu(BF4)2: 0.05 eq.
Time: 1h
Yield: 84% (119 mg)
Aspect: yellow oil

1H NMR (300 MHz, CDCl3):  = 9.73 (d, J = 2.1 Hz, 1H, H1), 7.42 – 7.13 (m, 9H, Harom), 6.53 –
6.47 (m, 2H, H3,4), 4.39 (dd, J = 5.6, 2.0 Hz, 1H, H2), 2.36 (s, 3H, H13).
13C NMR (75 MHz, CDCl ):  = 198.5, 137.6, 136.6, 134.1, 132.5, 129.9, 128.2, 128.6, 127.9,
3
126.5, 124.8, 61.6, 21.2.
HRMS (ESI) calculated for [M + H]+ (C17H17O): 237.12739, found: 237.12726.
IR (cm-1): 3031, 2952, 1721, 1689, 1513, 1453.

(E)-2-(4-methoxyphenyl)-4-phenylbut-3-enal (7n)

Amount of starting epoxide: 140.1 mg

Eq of Cu(BF4)2: 0.05 eq.
Time: 1h
S16
Yield: 79% (137 mg)
Aspect: yellow oil

1H NMR (300 MHz, CDCl3):  = 9.72 (d, J = 2.1 Hz, 1H, H1), 7.43 – 7.23 (m, 5H, H6,7,8), 7.20 (d,
J = 8.7 Hz, 2H, H10), 6.94 (d, J = 8.8 Hz, 2H, H11), 6.52 – 6.46 (m, 2H, H3,4), 4.38 (dd, J = 5.7, 2.0
Hz, 1H, H2), 3.81 (s, 3H, H13).
13C NMR (75 MHz, CDCl ):  = 198.4, 159.2, 136.6, 134.0, 130.0, 128.6, 127.9, 127.4, 126.4,
3
124.8, 114.7, 61.1, 55.3.
HRMS (ESI) calculated for [M + H]+ (C17H17O2): 253.12200, found: 253.12231.
IR (cm-1): 2836, 1687, 1606, 1510, 1247.

(E)-2-(3-Methoxyphenyl)-4-phenylbut-3-enal (7o)

The following description was made on a mixture of 7o and 9o.

Eq of Cu(BF4)2: 0.05 eq.
Time: 1h
Yield: 11% (Measured on the 1H NMR spectrum with an internal standard, dimethylterephtalate)
Aspect: yellow oil
1H NMR (300 MHz, CDCl3) δ = 9.74 (d, J = 2.1 Hz, 1H, H1), 7.48 – 7.27 (m, 7H, Harom), 6.97 –
6.79 (m, 2H, H12 and 13), 6.58 – 6.45 (m, 2H, H3 and 4), 4.43 – 4.36 (m, 1H, H2), 3.82 (s, 3H, H15).
13C NMR (75 MHz, CDCl ):  = 198.4, 160.4, 136.7, 134.5, 130.4, 129.3, 128.8, 128.7, 128.1,
3
126.6, 124.5, 121.32, 114.7, 62.1, 55.5.
HRMS (ESI) calculated for [M + H]+ (C17H17O2): 253.12231, found: 253.12189.

(E)-1-(4-methoxyphenyl)-4-phenylbut-3-en-1-one (9o)

The following description was made on a mixture of 7o and 9o.

1H NMR (300 MHz, CDCl3) δ = 7.48 – 7.27 (m, 6H, Harom), 6.97 – 6.79 (m, 3H, H10, 12 and 14), 6.58
– 6.45 (m, 2H, H3 and 4), 3.87 (d, J = 2.2 Hz, 2H, H2) ), 3.81 (s, 3H, H15).

(E)-4-phenyl-2-(o-tolyl)but-3-enal (7q)

S17
Amount of starting epoxide: 115 mg
Eq of Cu(BF4)2: 0.05 eq.
Time: 1h
Yield: 40% (determined by NMR)
Aspect: yellow oil

1H NMR (300 MHz, CDCl3):  = 9.75 (d, J = 1.4 Hz, 1, H1), 7.42 – 7.15 (m, 9H, Harom), 6.55 (dd, J
= 16.1, 6.4 Hz, 1H, H3), 6.37 (d, J = 16.2 Hz, 1H, H4), 4.61 (dt, J = 6.4, 1.3 Hz, 1H, H2), 2.36 (s,
2H, H15).
13C NMR (75 MHz, CDCl ) δ = 198.9, 137.2, 136.7, 134.1, 133.8, 131.3, 129.2, 128.7, 128.0,
3
127.9, 126.8, 126.5, 124.8, 58.7, 19.9.
HRMS (ESI) calculated for [M + H]+ (C17H17O): 237.12739, found: 237.12726.
IR (cm-1): 3027, 1721, 1689, 1494, 1453.

(E)-2,4-Bis(4-methoxyphenyl)but-3-enal (7r)

Amount of starting epoxide: 126.4 mg

Eq of Cu(BF4)2: 0.05 eq.
Time: 1h
Yield: 57% (determined by NMR)
Aspect: yellow oil

1H NMR (300 MHz, CDCl3):  = 9.70 (d, J = 2.2 Hz, 1H, H1), 7.34 – 7.28 (m, 1H, H6 or 10), 7.23 –
7.16 (m, 1H, H10 or 6), 6.96 – 6.91 (m, 1H, H11 or 7), 6.87 – 6.81 (m, 1H, H7 or 11), 6.46 – 6.29 (m, 1H,
H3 and 4), 4.34 (dd, J = 6.2, 2.2 Hz, 1H, H2), 3.81 (s, 3H, H13 or 14), 3.79 (s, 3H, H14 or 13).
13C NMR (75 MHz, CDCl ):  = 198.5, 159.4, 159.2, 133.5, 130.7, 130.0, 129.4, 127.6, 122.4,
3
114.6, 114.0, 61.1, 55.3. Signals for C13 and C12 are overlapping
HRMS (ESI): calculated for [M + H]+ (C18H19O3): 283.13287, found: 283.13274.

(E)-4-Phenyl-2-((E)-styryl)but-3-enal (7s)

S18
Eq of Cu(BF4)2: 0.05 eq.
Time: 1h
Yield: 15% (Measured on the 1H NMR spectrum with an internal standard, dimethylterephtalate)
Aspect: yellow oil
1H NMR (300 MHz, CDCl3) δ = 9.68 (d, J = 1.8 Hz, 1H, H1), 7.46 – 7.19 (m, 10H, Harom), 6.59 (d,
J = 16.2 Hz, 2H, H4), 6.33 (dd, J = 16.1, 7.4 Hz, 2H, H3), 4.09 – 4.01 (m, 1H, H2).
13C NMR (75 MHz, CDCl ):  = 198.5, 136.7, 134.8, 128.8, 128.2, 126.7, 123.4, 59.5.
3
HRMS (ESI) calculated for [M + H]+ (C18H17O): 249.12739, found: 249.12701.

(E)-4-Phenylbut-3-enal (7t)

Special procedure:

NaH (38wt% in mineral oil) (165 mg, 2.38 mmol, 3 eq) is added in a dry round bottom flask at 0°C.
The mineral oil is removed by washing NaH three times with n-hexane. Trimethylsulfonium iodide
(496 mg, 2.38 mmol, 3 eq.) and 3 mL of dry THF are introduced. Aldehyde (0.1 mL, 0.79 mmol, 1
eq.) in a mixture of 5 mL of dry DSMO and 2 mL of dry THF is added by small portions over 10
minutes. The reaction mixture is allowed to warm up to room temperature and stirred for 16h. Then,
the reaction mixture is diluted with diethylether and water. The phases are separated and the
aqueous phase is extracted twice with diethylether. The combined organic phases are washed with
brine, dried on MgSO4 and concentrated under reduced pressure to give the desired epoxide.
Epoxide (1 eq., 138 mg) and dry dichloromethane (9 mL) are introduced in a dry round-bottom
flask under argon. Then, Yb(OTf)3 (0.05 eq, 26 mg) is added and the mixture is stirred at room
temperature for 1 hour. Water is added to stop the reaction. The two layers are separated and the
aqueous one is extracted twice with dichloromethane. The combined organic layers are washed with
brine, dried over MgSO4 and concentrated under reduced pressure.

Yield: 52% (determined by NMR)

S19
Aspect: yellow oil
1H NMR (300 MHz, CDCl3) δ 9.75 (t, J = 1.9 Hz, 1H, H1), 7.44 – 7.21 (m, 5H), 6.54 (d, J = 16.0
Hz, 1H, H4), 6.28 (dt, J = 16.0, 7.0 Hz, 1H, H3), 3.37 – 3.32 (m, 2H, H2).
13C NMR (75 MHz, CDCl ) δ 199.6, 135.3, 128.7, 127.9, 126.7, 126.4, 119.3, 47.6.
3
HRMS (ESI) calculated for C10H10O: 146.07262, found: 146.07259.

2.2.2. Synthesis of enantioenriched β,γ-unsaturated aldehydes

2.2.2.1. General procedure

Chiral benzylic sulfonium salt (2 eq.) is dissolved in a 9/1 mixture of MeCN/H2O (8 mL/100 mg of
α,β-unsaturated aldehyde) in a round-bottom flask at 0°C. Aldehyde (1 eq., 150 mg) and KOH (2
eq.) are added and the mixture is allowed to warm up to room temperature and stirred for 24-72h.
Then, the reaction mixture is concentrated under reduced pressure and dissolved in
dichloromethane. Water is added and the two layers are separated. The aqueous one is extracted
twice with dichloromethane. The combined organic layers are washed with brine, dried over MgSO4
and concentrated under reduced pressure. The epoxide is purified by flash chromatography to
remove the chiral auxiliary.
Epoxide (1 eq., 100 mg) and dry dichloromethane (6 mL/100mg of epoxide) are introduced in a
round-bottom flask under argon. Cu(BF4)2 (0.10 eq.) is added and the reaction mixture is stirred at
room temperature for one hour. Water is added to stop the reaction. The two layers are separated
and the aqueous one is extracted twice with dichloromethane. The combined organic layers are
washed with brine, dried over MgSO4 and concentrated under reduced pressure.

2.2.2.2. Product descriptions

(E)-2,4-Diphenylbut-3-enal (7a*)

Eq of (CuBF4)2: 0.1 eq.

Yield: 41% (83 mg)
e.r. (epoxide intermediate): 98/2
e.r. (aldehyde): see 2.2.3.
For full details on the HPLC methods and the chromatograms, see 2.3.
Aspect: yellow oil

S20
1H NMR (300 MHz, CDCl3):  = 9.76 (d, J = 2.1 Hz, 1H, H1), 7.48 – 7.17 (m, 10H, Harom), 6.54 –
6.49 (m, 2H, H3 and 4), 4.43 (dd, J = 5.5, 2.0 Hz, 1H, H2).
13C NMR (75 MHz, CDCl ):  = 198.3, 136.5, 135.6, 134.3, 129.2, 129.0, 128.6, 128.0, 127.8,
3
126.5, 124.5, 61.9.

(E)-2,4,4-Triphenylbut-3-enal (7i*)

Eq of (CuBF4)2: 0.1 eq.

Yield: 12% (40 mg)
e.r.: see 2.2.3. for the determination of the e.r.
Aspect: yellow oil

1H NMR (300 MHz, CDCl3):  = 9.70 (d, J = 1.7 Hz, 1H, H1), 7.46 – 7.02 (m, 15H, Harom), 6.49 (d,
J = 10.1 Hz, 2H, H3), 4.43 (dd, J = 10.1, 1.5 Hz, 1H, H2).
13C NMR (75 MHz, CDCl ) δ 198.5, 146.0, 141.7, 139.2, 136.5, 129.8, 129.4, 128.8, 128.6, 128.4,
3
127.9, 127.8, 127.8, 127.6, 122.8, 59.5.

2.2.3. Synthesis of primary homoallylic alcohols

2.2.3.1. General procedure

The aldehyde (1 eq, 85 mg) is dissolved in MeOH (2 mL/100mg of aldehyde) in a round-bottom

flask. NaBH4 (2 eq) is added at 0°C and the reaction mixture is stirred at room temperature for 3h.
Then, the reaction mixture is concentrated under reduced pressure and dissolved in diethylether and
water. The two layers are separated and the aqueous one is extracted twice with diethylether. The
combined organic layers are washed with brine, dried over MgSO4 and concentrated under reduced
pressure. The alcohol is purified by flash column chromatography.

The eluent used for the chromatography column depends on the product and is given for each
synthesised alcohols in the next section.

S21
2.2.3.2. Product descriptions
(E)-2,4-diphenylbut-3-en-1-ol (12a*)

Yield: 54% (46 mg)

Aspect: colorless oil
e.r.: 74/26
For full details on the HPLC method and the chromatograms, see 2.3.
1H NMR (300 MHz, CDCl ) δ 7.41 – 7.19 (m, 10H, Harom), 6.54 (d, J = 16.0 Hz, 1H, H4), 6.38 (dd,
3
J = 15.9, 7.7 Hz, 1H, H3), 3.96 – 3.89 (m, 2H, H1), 3.71 (q, J = 7.2 Hz, 1H, H2), 1.50 (t, J = 6.4 Hz,
1H, H9).
13C NMR (75 MHz, CDCl ) δ 140.9, 137.1, 132.3, 129.8, 129.0, 128.7, 128.1, 127.6, 127.2, 126.4,
3
66.5, 52.0.

2,4,4-triphenylbut-3-en-1-ol (12i*)

Yield: 8% (7 mg)
e.r.: 71/29
For full details on the HPLC method and the chromatograms, see 2.3.
Aspect: colorless oil
1H NMR (300 MHz, CDCl ) δ 7.41 – 7.11 (m, 15H, Harom), 6.30 (d, J = 10.3 Hz, 1H, H3), 3.83 (d,
3
J = 6.7 Hz, 2H, H ), 3,70 (dt, J = 10,2, 6,8 Hz, 1H, H2), 1,34 (m, 1H, H17).
1

S22
2.3. HPLC analysis

2.3.1. Separation and analysis of 6a

An analytical method has been developed from a mixture of the four possible isomers of 6a.

Column: DAICEL CHIRALKPAK IA

Flow rate: 1 mL/min
Eluent: isohexane/ethanol (95/5)
Mode: isocratic
Injected volume: 5 μL
Observed chromatogram

The analytical method was then used to determine the e.r. of 6a-trans obtained with the chiral
sulfonium salt (see 2.2.2.).
Observed chromatogram

2.3.2. Separation and analysis of 12a

An analytical method has been developed from a racemic mixture of 12a.

S23
Column: DAICEL CHIRALKPAK IB
Flow rate: 1 mL/min
Eluent: isohexane/isopropanol (95/5)
Mode: isocratic
Injected volume: 5 μL
Observed chromatogram

The analytical method was then used to determine the e.r. of 12a* (see 2.2.3.2.)
Observed chromatogram

2.3.3. Separation and analysis of 12i

An analytical method has been developed from a racemic mixture of 12i

Column: DAICEL CHIRALKPAK IB

Flow rate: 1 mL/min
Eluent: isohexane/ethanol (95/5)
S24
Mode: isocratic
Injected volume: 5 μL
Observed chromatogram

The analytical method was then used to determine the e.r. of 12i* (see 2.2.3.2.)

Observed chromatogram

S25
2.4. NMR spectra

S26
S27
S28
S29
S30
S31
S32
S33
S34
S35
S36
S37
S38
S39
S40
S41
S42
S43
 3. Computational details
3.1. Methods

Calculations were carried out using the Orca 4.1.0 program package. Geometry
optimisations were performed at the M06-2X level of theory using the 6-31G(d) basis set.2 Solvent
effects were modelled by using the SMD solvation module3 as incorporated in Orca, using the
parameters for dichloromethane.
The stationary points were characterized by full calculation of vibrational frequencies at the
M06-2X/6-31+G(d)(CH2Cl2) level. These frequency calculations provided also thermal and
entropic contributions to free energy.
Gas phase electronic energies were obtained after single point calculations, at the M06-
2X/6-311+G(d,p) level of theory.
We have made a systematic attempt to locate all possible local minima (at the M06-2X/6- 31+G(d)
level), with the data presented referring to the lowest energy form.

3.2. Cartesian coordinates and energies

2
Hehre, W. J.; Ditchfield, R.; Pople, J. A. J. Chem. Phys. 1972, 56, 2257.
3
Marenich, A. V.; Cramer, C. J.; Truhlar, D. G. J. Phys. Chem. B 2009, 113, 6378
S44
6a-trans H -2.337796 -3.632650 2.877952
C -4.419731 0.177185 0.658730
E(M06-2X/6-31G(d)(CH2Cl2)) = -3181.86462 C -3.161332 0.282420 1.247616
E(M06-2X/6-311+G(d,p)) = -3182.519108 C -2.479169 -0.867182 1.642879
G(M06-2X/6-31G(d)(CH2Cl2)) = -3181.6964163 C -3.048666 -2.126188 1.414143
C -4.314113 -2.229312 0.830453
C 0.208324 -1.185763 1.736524 C -4.998933 -1.076421 0.459134
C 1.059014 -2.003584 0.840926 H -4.952872 1.073908 0.357638
H 1.065094 -3.077470 1.033273 H -2.712505 1.257733 1.409756
C 3.252571 -2.183151 -0.265869 H -1.506368 -0.785448 2.119199
C 2.152743 -1.475588 0.006902 H -4.755789 -3.208893 0.669621
H 1.990075 -0.489045 -0.422230 H -5.981477 -1.157848 0.007042
H 3.408813 -3.150028 0.212898 O -0.908879 -3.399935 1.350520
C 6.214893 -0.745393 -2.992426 Cu -0.897811 -2.358427 -0.399352
C 6.600062 -1.245644 -1.747337 F -2.173131 -1.579961 -3.716662
C 5.643233 -1.739776 -0.865025 B -1.662608 -1.051783 -2.587250
C 4.285915 -1.705863 -1.207473 F -1.431468 0.276177 -2.647072
C 3.907318 -1.210021 -2.462072 F -2.469393 -1.371710 -1.462034
C 4.867908 -0.738779 -3.352746 F -0.439032 -1.739258 -2.234476
H 6.963579 -0.366633 -3.681085 F 1.706872 -0.290069 -1.214857
H 7.647850 -1.249024 -1.462140 B 1.342219 -0.982082 -0.117877
H 5.942265 -2.128875 0.104701 F 1.289334 -2.374425 -0.372842
H 2.857762 -1.221803 -2.744221 F 2.079572 -0.714152 0.979695
H 4.563316 -0.373004 -4.328553 F -0.058086 -0.696532 0.182460
H 0.419419 -0.127613 1.858731 C -1.087270 -4.511096 -1.476059
C -2.449141 -3.459949 4.225618 C -2.101672 -4.302893 -0.594218
C -1.070241 -3.573499 4.405743 H -3.106862 -4.085743 -0.946669
C -0.187003 -2.804733 3.650290 H -0.090409 -4.745963 -1.088444
C -0.684922 -1.889596 2.723767 C -1.443873 -4.264031 -5.714911
C -2.081714 -1.731684 2.575634 C -0.208211 -4.059046 -5.100971
C -2.957250 -2.531298 3.322843 C -0.092638 -4.171622 -3.720201
H -3.125763 -4.103177 4.778696 C -1.220085 -4.467269 -2.940448
H -0.676548 -4.298636 5.110852 C -2.456003 -4.677251 -3.564936
H 0.885636 -2.939614 3.751508 C -2.564133 -4.581911 -4.947098
H -2.485728 -0.936621 1.943795 H -1.531999 -4.186003 -6.794920
H -4.028991 -2.434455 3.176301 H 0.663838 -3.812398 -5.698654
O -0.252562 -1.501007 0.376130 H 0.867389 -4.000752 -3.238871
Cu -1.682094 -2.818749 0.594651 H -3.327454 -4.936494 -2.971592
F -1.027712 -4.685840 1.518430 H -3.522275 -4.760084 -5.424987
B -2.272853 -5.299455 1.258418 H -1.659985 -5.393923 1.295044
F -2.841531 -5.774719 2.382731
F -3.053119 -4.137373 0.791560
F -2.181737 -6.192690 0.258858 TS-open-Ph-trans
F -2.565909 -4.533477 -2.241984
B -1.733330 -3.514502 -1.951954 E(M06-2X/6-31G(d)(CH2Cl2)) = -3181.896775
F -0.788751 -3.912714 -0.961143 E(M06-2X/6-311+G(d,p)) = -3182.4921187
F -1.107330 -2.980956 -3.019860 G(M06-2X/6-31G(d)(CH2Cl2)) = -3181.6747442
F -2.459164 -2.477101 -1.248258
C -0.143812 -0.760178 2.154807
6a-cis C 1.181882 -1.422545 1.963435
H 1.221705 -2.491447 2.174663
E(M06-2X/6-31G(d)(CH2Cl2)) = -3181.921728 C 3.277431 -1.780939 0.959789
E(M06-2X/6-311+G(d,p)) = -3182.524712223 C 2.270395 -0.888055 1.291176
G(M06-2X/6-31G(d)(CH2Cl2)) = -3181.697124 H 2.279676 0.151566 0.979179
H 3.193055 -2.783193 1.379309
C -2.298421 -3.351744 1.829086 C 6.581255 -1.339111 -1.621918
C -1.877376 -4.411022 0.888132 C 6.517726 -2.421140 -0.741049
S45
 C 5.427454 -2.549575 0.105310 F -0.518836 -0.538471 -2.857688
C 4.411361 -1.569653 0.108351 B -0.494983 -0.078914 -1.589939
C 4.495806 -0.472574 -0.775669 F -0.151636 1.214543 -1.481829
C 5.569790 -0.371910 -1.644993 F -1.698534 -0.360138 -0.906286
H 7.420237 -1.253956 -2.306368 F 0.440366 -0.898176 -0.804507
H 7.307722 -3.165530 -0.731051 F 1.617342 1.356861 0.783721
H 5.350257 -3.397707 0.780396 B 0.832387 0.756263 1.702860
H 3.698783 0.264855 -0.807840 F 1.111864 -0.657234 1.731370
H 5.621154 0.450047 -2.351612 F 0.944705 1.271127 2.946760
H -0.091923 0.273299 2.510566 F -0.531695 0.775589 1.278981
C -2.963144 -3.473224 4.012653 C -0.511137 -3.537697 -1.194553
C -1.632594 -3.464712 4.437044 C -1.624954 -3.248192 -0.379289
C -0.725671 -2.553479 3.906105 H -2.513351 -2.791378 -0.807766
C -1.134433 -1.629846 2.938909 H 0.408529 -3.845359 -0.693424
C -2.488524 -1.615573 2.540338 C -0.207015 -2.868678 -5.318406
C -3.395125 -2.538402 3.079419 C 0.951001 -2.976137 -4.541653
H -3.654674 -4.210771 4.407447 C 0.837981 -3.257775 -3.191655
H -1.290306 -4.196149 5.162468 C -0.444075 -3.374639 -2.597699
H 0.312653 -2.583485 4.224742 C -1.607843 -3.243545 -3.396951
H -2.847937 -0.850678 1.851598 C -1.481201 -3.020676 -4.753222
H -4.428405 -2.531617 2.745799 H -0.119866 -2.668156 -6.382829
O -0.472956 -0.829539 0.777992 H 1.926512 -2.842447 -4.996454
Cu -1.392521 -2.463698 0.638162 H 1.723808 -3.346853 -2.569074
F -0.074374 -4.081340 1.330033 H -2.589983 -3.359417 -2.950436
B -1.085485 -5.047842 1.126499 H -2.362905 -2.952020 -5.381064
F -1.387576 -5.684403 2.277496 H -0.748129 -4.086520 1.388922
F -2.218359 -4.203377 0.744803
F -0.783177 -5.868636 0.103824
F -2.182032 -4.180721 -2.225228 TS-open’
B -1.633218 -2.975356 -1.950743
F -0.484727 -3.135266 -1.122589 E(M06-2X/6-31G(d)(CH2Cl2)) = -3181.883984
F -1.318062 -2.255011 -3.052361 E(M06-2X/6-311+G(d,p)) = -3182.480139
F -2.512806 -2.221526 -1.103590 G(M06-2X/6-31G(d)(CH2Cl2)) = -3181.661602

C 0.027287 -1.463333 1.248106

TS-open-Ph-cis C 1.234039 -2.225362 0.816293
H 1.574449 -2.928492 1.592563
E(M06-2X/6-31G(d)(CH2Cl2)) = -3181.8935144 C 3.648564 -2.004611 0.234211
E(M06-2X/6-311+G(d,p)) = -3182.4893136 C 2.417869 -1.461798 0.236487
G(M06-2X/6-31G(d)(CH2Cl2)) = -3181.6713163 H 2.185028 -0.591699 -0.378473
H 3.837588 -2.832000 0.921775
C -2.448154 -2.837904 2.005045 C 6.961388 -1.101443 -2.317190
C -1.589397 -3.527707 0.978916 C 7.167291 -1.702067 -1.075275
H -2.631558 -3.490768 2.864345 C 6.085902 -1.967652 -0.239686
C -6.133078 -1.203004 0.491082 C 4.785621 -1.616252 -0.626791
C -5.029053 -0.372195 0.667479 C 4.588577 -1.020535 -1.880505
C -3.836730 -0.891898 1.173246 C 5.668712 -0.765522 -2.718837
C -3.743562 -2.247850 1.490175 H 7.802103 -0.917643 -2.979473
C -4.852452 -3.077781 1.314125 H 8.169185 -1.983285 -0.765525
C -6.044304 -2.557304 0.819648 H 6.243632 -2.458153 0.716661
H -7.064427 -0.798233 0.107275 H 3.582060 -0.800564 -2.231392
H -5.090164 0.682855 0.415840 H 5.495372 -0.336824 -3.700384
H -2.989666 -0.233152 1.339059 H -0.004225 -0.381214 1.121836
H -4.778727 -4.131135 1.576528 C -3.566113 -3.396412 2.079147
H -6.905097 -3.206988 0.696044 C -2.406294 -4.171236 1.916994
O -1.473528 -1.875760 2.317674 C -1.197670 -3.550593 1.690045
Cu -0.602458 -1.253338 0.783029 C -1.142675 -2.123407 1.618260
S46
 C -2.330840 -1.359265 1.791952 O -0.581340 -0.379982 0.912271
C -3.533434 -1.996813 2.022058 Cu -1.650346 -1.884591 0.678518
H -4.515881 -3.896555 2.246688 F -1.598610 -4.121188 0.951224
H -2.468113 -5.253679 1.953857 B -2.952390 -4.239291 0.622468
H -0.305133 -4.139719 1.509575 F -3.652222 -4.882602 1.584650
H -2.276798 -0.277025 1.717939 F -3.368210 -2.839039 0.590075
H -4.447314 -1.426872 2.143807 F -3.114822 -4.760505 -0.616127
O 0.645255 -2.875095 -0.304927 F -1.388730 -3.055771 -2.791162
Cu 2.162274 -3.346666 -1.270976 B -0.900160 -2.177710 -1.886824
F 1.965183 -2.806216 -3.286043 F -0.280614 -2.830534 -0.809734
B 3.130077 -3.544638 -3.665869 F -0.026683 -1.276198 -2.427612
F 3.988451 -2.770017 -4.348587 F -1.987296 -1.472208 -1.260090
F 3.685045 -3.849709 -2.346851
F 2.790600 -4.695789 -4.275723
F 2.411937 -7.003854 -0.674119 10a’
B 1.779307 -5.834805 -0.421466
F 1.341461 -5.243016 -1.638708 E(M06-2X/6-31G(d)(CH2Cl2)) = -3181.8901930
F 0.735144 -5.956788 0.443250 E(M06-2X/6-311+G(d,p)) = -3182.4880220
F 2.704490 -4.881878 0.091595 G(M06-2X/6-31G(d)(CH2Cl2)) = -3181.6683854

C 1.172006 -0.452291 1.821992

10a C 2.581945 -0.886362 2.053589
H 3.001217 -0.175751 2.790094
E(M06-2X/6-31G(d)(CH2Cl2)) = -3181.9092648 C 4.500718 -1.165545 0.412731
E(M06-2X/6-311+G(d,p)) = -3182.505131755 C 3.284576 -0.639654 0.679127
G(M06-2X/6-31G(d)(CH2Cl2)) = -3181.6873056 H 2.733552 -0.124867 -0.105223
H 5.059722 -1.639799 1.226458
C 0.213398 -0.616352 2.022808 C 6.302965 -1.466691 -3.451432
C 1.638586 -0.873330 1.646897 C 6.727832 -2.277432 -2.400228
H 2.389856 -0.859492 2.436857 C 6.159363 -2.131741 -1.137684
C 3.354665 -1.480555 0.127892 C 5.151661 -1.183811 -0.914032
C 2.012801 -1.143008 0.359814 C 4.736891 -0.367735 -1.974521
H 1.264070 -1.154061 -0.426305 C 5.312050 -0.508155 -3.232898
H 4.042321 -1.348715 0.963196 H 6.739115 -1.581316 -4.439204
C 5.150688 -3.177338 -3.265781 H 7.496496 -3.026996 -2.563311
C 5.927334 -2.836662 -2.154687 H 6.480681 -2.774764 -0.321215
C 5.316364 -2.264506 -1.052761 H 3.961561 0.377823 -1.821893
C 3.922018 -2.014804 -1.058007 H 4.980298 0.126977 -4.048647
C 3.150579 -2.350156 -2.199454 H 1.060419 0.622793 1.676648
C 3.769781 -2.934531 -3.289819 C -2.122878 -2.642917 0.575292
H 5.625664 -3.642567 -4.124671 C -1.104281 -3.335304 1.247281
H 6.995019 -3.028300 -2.153574 C -0.034692 -2.644948 1.776575
H 5.895716 -2.002055 -0.172128 C 0.031946 -1.221841 1.621854
H 2.080876 -2.160400 -2.215203 C -1.062304 -0.536663 1.001476
H 3.189985 -3.211072 -4.163803 C -2.115247 -1.245381 0.464807
H 0.225445 0.256368 2.702151 H -2.943574 -3.203377 0.135825
C -1.674682 -4.030393 3.943799 H -1.154120 -4.415533 1.333430
C -2.401488 -2.888932 3.623111 H 0.753891 -3.159391 2.308869
C -1.756436 -1.784143 3.056956 H -1.020746 0.544887 0.913762
C -0.369405 -1.821893 2.799386 H -2.923727 -0.733307 -0.044349
C 0.348068 -2.977879 3.125794 O 2.754457 -2.197965 2.443496
C -0.301216 -4.066020 3.705298 Cu 3.060771 -3.018256 0.787701
H -2.177735 -4.895931 4.363067 F 1.448394 -2.562473 -0.632569
H -3.472716 -2.855197 3.795544 B 2.121014 -3.233536 -1.678797
H -2.316470 -0.866209 2.876795 F 2.405230 -2.383154 -2.687480
H 1.412566 -3.042381 2.918439 F 3.362626 -3.623117 -1.024146
H 0.268168 -4.958769 3.946129 F 1.453321 -4.343052 -2.054922
S47
 F 3.302279 -6.316605 -0.028828 TS-mig-Ph-cis
B 3.140630 -5.639435 1.130418
F 1.989577 -4.793029 1.044385 E(M06-2X/6-31G(d)(CH2Cl2)) = -3181.8973991
F 3.054259 -6.433700 2.220744 E(M06-2X/6-311+G(d,p)) = -3182.4998881
F 4.199206 -4.689582 1.296726 G(M06-2X/6-31G(d)(CH2Cl2)) = -3181.673568

C 1.023615 -0.144741 -1.467928

TS-mig-Ph-trans C 1.708003 0.438945 -0.362166
H 2.356752 1.294626 -0.529659
E(M06-2X/6-31G(d)(CH2Cl2)) = -3181.8951362 C 2.566688 0.069218 1.868568
E(M06-2X/6-311+G(d,p)) = -3182.50425637 C 1.676977 -0.236839 0.895773
G(M06-2X/6-31G(d)(CH2Cl2)) = -3181.6728363 H 1.057033 -1.126194 0.941472
H 3.197409 0.948780 1.742822
C -0.153214 1.463964 -1.456440 C 3.497837 -2.348747 5.235533
C 0.628786 0.581372 -0.573076 C 4.285189 -1.243599 4.916472
H 0.198543 0.316754 0.393275 C 3.949709 -0.447489 3.827030
C 2.713841 -0.452983 0.087727 C 2.829639 -0.754206 3.041305
C 1.934411 0.144389 -0.870090 C 2.039023 -1.868711 3.374355
H 2.325839 0.326054 -1.867020 C 2.371981 -2.656482 4.466282
H 2.313724 -0.544905 1.097666 H 3.757802 -2.973069 6.084737
C 6.744802 -1.649539 -0.436023 H 5.161728 -1.006435 5.510500
C 6.250509 -1.380498 0.841539 H 4.560178 0.412635 3.565253
C 4.913521 -1.040017 1.007981 H 1.162895 -2.118304 2.783332
C 4.070976 -0.917484 -0.113277 H 1.759112 -3.517064 4.715815
C 4.579694 -1.199347 -1.396765 H 1.380760 0.143203 -2.462573
C 5.905085 -1.575350 -1.551928 C -2.205632 2.849107 -1.040873
H 7.786736 -1.927909 -0.564598 C -1.163179 3.069994 -1.942067
H 6.908275 -1.440235 1.702935 C -0.048737 2.236813 -1.941329
H 4.518982 -0.832667 1.998889 C -0.006162 1.159395 -1.046850
H 3.924374 -1.154850 -2.261628 C -1.045290 0.937889 -0.129028
H 6.289787 -1.810533 -2.538948 C -2.144666 1.791179 -0.131280
H 0.317260 1.558585 -2.441533 H -3.075052 3.499361 -1.052864
C 1.112726 4.831302 0.995348 H -1.229580 3.874726 -2.667343
C 1.857508 4.492566 -0.138776 H 0.744392 2.378485 -2.670135
C 1.499329 3.390804 -0.903173 H -0.997531 0.107882 0.571427
C 0.366566 2.646950 -0.551507 H -2.955822 1.623756 0.570020
C -0.369230 2.976643 0.594308 O 0.415847 -1.324626 -1.322551
C 0.003719 4.071159 1.364050 Cu -1.258702 -0.870473 -2.068289
H 1.399098 5.691641 1.591875 F -2.260318 -2.688207 -2.568031
H 2.716483 5.090384 -0.424126 B -3.116710 -2.615687 -1.439617
H 2.076578 3.113718 -1.781730 F -3.060948 -3.745359 -0.706535
H -1.240424 2.393269 0.864759 F -2.514951 -1.527871 -0.684954
H -0.570170 4.326232 2.249471 F -4.361013 -2.250392 -1.813084
O -1.509404 1.400683 -1.529531 F -2.589629 -0.462384 -5.130893
Cu -2.687321 0.298601 -0.667717 B -2.011656 0.309413 -4.198958
F -1.617055 -0.826655 0.857210 F -0.704316 -0.209652 -3.864880
B -2.061743 0.003500 1.911946 F -1.937280 1.615349 -4.487993
F -0.993627 0.608910 2.489867 F -2.687896 0.115675 -2.924713
F -2.838645 1.008140 1.204372
F -2.850779 -0.664130 2.772105
F -3.124837 -2.940678 0.037651 TS-mig-styryl
B -3.643418 -2.071064 -0.844413
F -2.615722 -1.477905 -1.653749 E(M06-2X/6-31G(d)(CH2Cl2)) = -3181.8816174
F -4.629007 -2.564168 -1.610977 E(M06-2X/6-311+G(d,p)) = -3182.4916466
F -4.122158 -0.880103 -0.147448 G(M06-2X/6-31G(d)(CH2Cl2)) = -3181.65990

C -1.308032 -1.632167 0.688871

S48
 C -0.499441 -1.879332 -0.519130 C 5.567586 -3.403948 -1.685142
H -0.842226 -2.755523 -1.079079 C 4.993611 -2.766422 -0.597139
C 1.226238 -3.539974 0.303809 C 3.632978 -2.387892 -0.634397
C 0.703501 -2.301320 0.357295 C 2.844647 -2.705224 -1.763127
H 1.200580 -1.499846 0.903956 C 3.416485 -3.384957 -2.826418
H 0.736809 -4.289110 -0.318477 H 5.218953 -4.246617 -3.632415
C 4.993835 -4.624504 1.975659 H 6.618606 -3.672160 -1.671545
C 4.600340 -5.115384 0.729869 H 5.586156 -2.530378 0.282337
C 3.351632 -4.784257 0.216247 H 1.785973 -2.466327 -1.768262
C 2.499589 -3.923986 0.924361 H 2.812142 -3.664549 -3.682705
C 2.903527 -3.428938 2.173940 H -0.039251 0.856608 1.557600
C 4.140203 -3.790872 2.700351 C -0.365142 0.087655 6.446256
H 5.962957 -4.895242 2.382845 C -1.440796 -0.228989 5.625265
H 5.265886 -5.756319 0.159582 C -1.296731 -0.181776 4.233388
H 3.039126 -5.161147 -0.753619 C -0.058766 0.161356 3.651863
H 2.235080 -2.786655 2.741880 C 0.995830 0.528309 4.490968
H 4.438741 -3.425657 3.677976 C 0.841137 0.496394 5.874415
H -0.978510 -0.799802 1.308226 H -0.461043 0.020859 7.525739
C -4.808050 -3.440740 2.091885 H -2.391560 -0.528885 6.055909
C -4.059584 -2.623613 2.947054 H -2.173352 -0.337509 3.601965
C -2.880625 -2.064631 2.488945 H 1.955044 0.813809 4.066420
C -2.419841 -2.352985 1.177990 H 1.680894 0.760748 6.509813
C -3.179985 -3.199575 0.333548 O -0.721213 -1.099944 1.734177
C -4.375147 -3.724218 0.789969 Cu -0.874033 -2.260198 3.183306
H -5.752758 -3.848984 2.437337 F 0.506275 -2.516316 5.020143
H -4.416348 -2.412459 3.949164 B -0.334341 -3.522111 5.489381
H -2.300962 -1.396518 3.119696 F -0.745983 -3.292563 6.754840
H -2.851622 -3.388563 -0.682900 F -1.499281 -3.387571 4.593988
H -4.985297 -4.337810 0.136502 F 0.194017 -4.751868 5.296235
O -0.224403 -0.833139 -1.359000 F 0.481523 -5.483476 1.978645
Cu 0.151550 0.875452 -0.801594 B 0.266135 -4.174000 1.710655
F 2.007814 0.806811 -0.038588 F 0.937326 -3.354093 2.645154
B 2.073795 2.226514 0.206095 F 0.613175 -3.818944 0.445779
F 3.152137 2.761565 -0.386320 F -1.117631 -3.854764 1.946932
F 0.869417 2.647824 -0.501882
F 1.962840 2.487430 1.516454
F -1.813277 2.987663 1.332493 7a
B -1.680328 1.700057 0.963534
F -0.413932 1.186575 1.324979 E(M06-2X/6-31G(d)(CH2Cl2)) = -3181.9290798
F -2.655242 0.881120 1.436703 E(M06-2X/6-311+G(d,p)) = -3182.5377020
F -1.658682 1.602358 -0.485123 G(M06-2X/6-31G(d)(CH2Cl2)) = -3181.704668

C 0.447100 0.924921 -1.490808

TS isomerization cis-trans C 1.053556 0.654886 -0.140618
H 0.403096 0.001787 0.452567
E(M06-2X/6-31G(d)(CH2Cl2)) = -3181.8948513 C 3.079830 -0.657969 0.600684
E(M06-2X/6-311+G(d,p)) = -3182.4957987 C 2.426907 0.041084 -0.333593
G(M06-2X/6-31G(d)(CH2Cl2)) = -3181.6710223 H 2.933260 0.282517 -1.267855
H 2.610769 -0.845421 1.567449
C 0.126982 -0.057717 2.142086 C 7.191677 -1.793227 0.171651
C 1.477880 -0.663095 1.854728 C 6.694784 -1.382961 1.408997
H 2.092679 -0.982666 2.696704 C 5.348261 -1.054396 1.549081
C 3.087407 -1.738830 0.514351 C 4.482510 -1.107686 0.446800
C 1.911787 -0.993468 0.594180 C 4.988817 -1.537291 -0.787834
H 1.310362 -0.767974 -0.280903 C 6.332067 -1.878280 -0.923724
H 3.669260 -1.833263 1.431321 H 8.241129 -2.052561 0.064021
C 4.775673 -3.719945 -2.792290 H 7.359382 -1.315593 2.265848
S49
H 4.967677 -0.731551 2.515208
H 4.319581 -1.620347 -1.640171
H 6.707354 -2.214789 -1.885662
H 1.141987 1.219290 -2.285873
C 1.099271 4.439036 2.034882
C 2.215046 3.605358 2.055269
C 2.224587 2.419438 1.322917
C 1.110284 2.049216 0.566923
C 0.008311 2.910179 0.521220
C -0.003610 4.089879 1.258882
H 1.088186 5.353640 2.618825
H 3.084799 3.870835 2.648002
H 3.095879 1.775590 1.359766
H -0.866698 2.666318 -0.070485
H -0.880836 4.728920 1.225538
O -0.752925 0.912833 -1.798932
Cu -2.218160 0.326109 -0.699602
F -1.493348 -2.896521 -2.261455
B -2.153225 -2.213871 -1.310356
F -3.096997 -2.913434 -0.655239
F -1.258905 -1.599888 -0.403081
F -2.790502 -1.034221 -1.932124
F -3.474677 0.803216 2.590772
B -2.770187 0.038876 1.754026
F -1.717053 0.825378 1.114468
F -2.250607 -1.078464 2.268156
F -3.553078 -0.261835 0.561758

S50