Ol8b00313 Si 001

Nickel-Catalyzed System for the Cross-
Coupling of Alkenyl Methyl Ethers with

Grignard Reagents under Mild Conditions
T. Hostier,a Z. Neouchy,a V. Ferey,† D. Gomez Pardoa and J. Cossy*a
a
Laboratoire de Chimie Organique, Institute of Chemistry, Biology and Innovation (CBI), UMR 8231,
ESPCI Paris /CNRS/PSL Research University, 10 rue Vauquelin, Paris 75231 Cedex 05, France
† Chemistry and Biotechnology Development, SANOFI, 371 rue du Professeur Blayac, 34184
Montpellier Cedex 04, France
* E-mail: [email protected]
Supporting Information
Table of contents:
General information…………………………………………………………………………...S-2
1. Synthesis of alkenyl methyl ethers by Wittig reaction……………………..S-3
2. Nickel-catalyzed Kumada coupling of alkenyl methyl ethers……….....S-19
3. Stereoselectivity studies of the cross-coupling reaction………………….S-46
4. Copies of the 1H and 13C NMR spectra…………………………………………….S-47
S-1
General information
All reactions were carried out under an argon atmosphere unless otherwise specified. Flasks were
oven-dried at 120 °C and cooled under argon prior to use. CH2Cl2 was distilled over calcium hydride,
THF and Et2O were distilled over sodium/benzophenone prior to use. Toluene was pre-dried by
passing through a column on alumina, stirred for 24 h on calcium hydride, then fractionally distilled
under argon and stored over molecular sieves (4Å) under argon. Toluene was degassed by bubbling
with argon for 1 h before each use. The concentration of Grignard reagents was determined by
titration with salicylaldehyde phenylhydrazone (Love’s reagent) in THF.1 Anhydrous Ni(OAc)2 was
prepared by heating Ni(OAc)2·4H2O at 100 °C under vacuum until the color changed from greenish
blue (hydrate) to greenish yellow (anhydrous). All other commercially available chemicals were
purchased from Aldrich and used directly without purification.
1
H NMR Spectra were recorded on a Bruker Avance 400 at 400 MHz. The chemical shifts δ are
reported in ppm relative to tetramethylsilane (TMS) or residual protonated solvents (TMS: δH = 0.00
ppm, CHCl3: δH = 7.26 ppm, C6H6: δH = 7.16 ppm). The multiplicity is designated by the following
abbreviations: s = singlet, d = doublet, t = triplet, q = quartet, quin = quintet, m = multiplet, br =
broad, app = apparent. Coupling constants J are reported in Hertz (Hz).
13
C NMR Spectra were recorded on a Bruker Avance 400 at 100 MHz. The chemical shifts δ are
reported in ppm relative to the solvent as an internal indicator (CDCl3 δ 77.16 ppm, C6D6 δ 128.06
ppm). Coupling constants J are reported in Hertz (Hz).
TLCs were performed on Merck 60F254 silica gel plates and visualized with UV lamp (254 nm), and by
treatment with a solution of p-anisaldehyde/H2SO4/AcOH in ethanol followed by heating. Flash
column chromatographies were performed with Merck Geduran Si 60 silica gel (40-63 m).
IR-Spectra were recorded on a Bruker TENSORTM 27 (IRTF). The samples were prepared as neat films
or as fine powders. Only selected absorbances (νmax) are reported, and wave numbers are reported in
cm–1. Mass spectra with electronic impact (MS-EI) were recorded from a Shimadzu GCMS-QP 2010S
(70 eV). High resolution mass spectra (HRMS) were performed by the Centre Regional de
Microanalyse (Université Pierre et Marie Curie VI, Paris, France). Melting points were determined on
a Büchi Melting Point M-560 apparatus with open capillaries and are uncorrected. Organic
compounds were named according to IUPAC rules.
1
Love, B. E.; Jones, E. G. J. Org. Chem. 1999, 64, 3755–3756.
S-2
1. Synthesis of alkenyl methyl ethers by Wittig reaction
General procedure A
To a suspension of (methoxymethyl)triphenylphosphonium chloride (1.2 equiv) in THF (c = 0.25 M) at

0 °C, was added dropwise a 1.0 M solution of lithium bis(trimethylsilyl)amide (1.3 equiv) in THF. The
resulting dark red solution was stirred at 0 °C for 30 min, then a solution of the aldehyde (1 equiv) in
THF (c = 1 M) was added dropwise at 0 °C over 15 min. The reaction mixture was allowed to warm to
rt. After 16 h, an aqueous saturated solution of NH4Cl was added and the resulting mixture was
stirred for 15 min. Both layers were separated and the aqueous phase was extracted with EtOAc (3
x). The combined organic extracts were washed with H2O and brine, dried over anhydrous Na2SO4,
filtered and concentrated under reduced pressure. The crude product was purified by flash column
chromatography on silica gel using a mixture of Petroleum ether (PE)/Et2O or PE/EtOAc as the eluent
to afford the desired product as a mixture of stereoisomers (E) and (Z).
General procedure B
The (E)-alkenyl methyl ethers (E)-1c, (E)-1f, (E)-1g and (E)-1p were prepared according to described
procedure.2 To a solution of methoxymethyldiphenylphosphine oxide (1.21.4 eq) in dry THF (c =
0.14 M) at 0 °C, was added dropwise a 0.66 M solution of LDA (1.4 eq) in THF and the resulting
mixture was stirred for 1h. To the mixture was added dropwise a solution of aldehyde (1 eq) in THF (c
= 1 M) at ‒ 78 °C and the resulting mixture was stirred for 1h. The reactionnal medium was allowed
to warm to room temperature and was quenched with an aqueous saturated solution of NH4Cl under
stirring. Both layers were separated and the aqueous phase was extracted with Et2O (3 x). The
combined organic extracts were washed with water and brine, dried over anhydrous Na2SO4, filtered
and concentrated under reduced pressure. The crude product was purified by flash column
chromatography on silica gel using a mixture of Pentane/EtOAc as the eluent to the desired (±)-
((1S,2R)-2-hydroxy-1-methoxy-2-(aryl)ethyl)diphenylphosphine oxide. To a solution of the latter
compound (1 equiv) in dry THF (c = 0.05 M), NaH (34 equiv) was added at room temperature and
the resulting mixture was stirred for 24 h. The precipitate was filtered and washed with Et2O. The
filtrate was then concentrated under reduced pressure. The crude product was purified by flash
column chromatography on silica gel using a mixture of PE/Et2O as the eluent to afford the desired
(E)-alkenyl methyl ether. Compounds (E)-1c and (E)-1f are already described from E/Z mixture
obtained by procedure A.
2
Earnshaw, C.; Wallis, C.J.; Warren, S. JCS Perkin I 1979, 3099‒3106.
S-3
(2-Methoxyethenyl)benzene (1a)
Compound 1a was synthesized from benzaldehyde (1.02 mL, 10 mmol) according to procedure A.
Purification by flash column chromatography (PE 100%) afforded 1a (842 mg, 6.28 mmol, 63%) as a
clear oil and as a mixture of (E)-1a and (Z)-1a in a ratio E/Z = 55:45. The (E)- and (Z)-isomers were
partially separated by column chromatography (PE 100%). The spectral data are given for each
isomer (E)-1a and (Z)-1a.
(E)-(2-Methoxyethenyl)benzene ((E)-1a)3
Formula: C9H10O MW= 134.18 g.mol–1
Compound (E)-1a was isolated as a clear oil.
IR (neat): νmax 3060, 3023, 2955, 2932, 2832, 1639, 1600, 1575, 1491, 1461, 1450, 1330, 1312, 1235,
1190, 1149, 1123, 1073, 997, 933 cm–1.
1
H NMR (CDCl3, 400 MHz): δ 7.287.21 (m, 4H), 7.13 (m, 1H), 7.04 (d, J = 13.0 Hz, 1H), 5.81 (d, J =
13.0 Hz, 1H), 3.68 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 149.0, 136.5, 128.7 (2C), 125.8, 125.2 (2C), 105.2, 56.6.
MS (EI, 70 eV): m/z (relative intensity) = 134 (M+•, 56), 119 (11), 91 (100), 65 (23), 51 (11).
(Z)-(2-Methoxyethenyl)benzene ((Z)-1a)3
Formula: C9H10O MW = 134.18 g.mol–1
Compound (Z)-1a was isolated as a clear oil.
IR (neat): νmax 3029, 2934, 2867, 2828, 1650, 1600, 1492, 1455, 1444, 1401, 1300, 1269, 1203, 1093,
1074, 1030, 982, 912 cm–1.
1
H NMR (CDCl3, 400 MHz): δ 7.577.55 (m, 2H), 7.307.24 (m, 2H), 7.13 (m, 1H), 6.13 (d, J = 7.0 Hz,
1H), 5.22 (d, J = 7.0 Hz, 1H), 3.77 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 148.1, 136.0, 128.32 (2C), 128.30 (2C), 125.9, 105.8, 60.8.
3
Cuthbertson, J.; Wilden, J. D. Tetrahedron 2015, 71, 4385‒4392.
S-4
1-(Benzyloxy)-4-(2-methoxyethenyl)benzene (1b)
Compound 1b was synthesized from 4-benzyloxybenzaldehyde (1.09 g, 5.00 mmol) according to

procedure A. Purification by flash column chromatography (PE/Et2O = 98:2) afforded 1b (377 mg,
1.57 mmol, 31%) as a white solid and as a mixture of (E)-1b and (Z)-1b in a ratio E/Z = 58:42. As the
two sets of signals in the 1H and 13C NMR spectra are differentiated, an independent description for
(E)-1b and (Z)-1b is reported. Both E- and Z-isomers are differentiated by GC, MS data for both
isomers are reported.
For both (E)- and (Z)-isomers:
IR (solid state): νmax 3034, 2934, 2859, 2832, 1641, 1606, 1509, 1454, 1383, 1314, 1238, 1176, 1152,
1094, 1038, 1025, 941 cm–1.
(E)-1-(Benzyloxy)-4-(2-methoxyethenyl)benzene ((E)-1b)4
Formula: C16H16O2 MW = 240.30 g.mol–1

1
H NMR (CDCl3, 400 MHz): δ 7.43–7.41 (m, 5H), 7.15 (d, J = 8.5 Hz, 2H), 6.92 (d, J = 12.9 Hz, 1H), 6.92–
6.87 (m, 2H), 5.77 (d, J = 13.0 Hz, 1H), 5.04 (s, 2H), 3.65 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 157.2, 147.8, 137.26, 129.3, 128.70 (2C), 128.1, 127.6 (2CH), 126.31
(2C), 115.3 (2C), 104.7, 70.2, 56.6.
(Z)-1-(Benzyloxy)-4-(2-methoxyethenyl)benzene ((Z)-1b)4

1
H NMR (CDCl3, 400 MHz): δ 7.50 (d, J = 8.9 Hz, 2H), 7.43–7.31 (m, 5H), 6.92–6.87 (m, 2H), 6.05 (d, J =
7.0 Hz, 1H), 5.17 (d, J = 7.0 Hz, 1H), 5.05 (s, 2H), 3.74 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 156.9, 146.6, 137.32, 129.5 (2C), 129.2, 128.68 (2C), 128.0, 127.6 (2C),
114.8 (2C), 105.3, 70.1, 60.6.
4
Ermolat’ev, D. S.; Bariwal, J. B.; Steenackers, H. P. L.; De Keersmaecker, S. C. J.; Van der Eycken, E. V. Angew.
Chem., Int. Ed. 2010, 49, 9465–9468.
S-5
1-Methoxy-4-(2-methoxyethenyl)benzene (1c)
Compound 1c was synthesized from 4-methoxybenzaldehyde (0.620 mL, 5.00 mmol) according to
procedure A. Purification by flash column chromatography (PE/Et2O = 99:1 then 98:2) afforded 1c
(798 mg, 4.86 mmol, 97%) as a pale yellow oil and as a mixture of (E)-1c and (Z)-1c in a ratio
E/Z = 48:52. As the two sets of signals in the 1H and 13C NMR spectra are differentiated, an
independent description for (E)-1c and (Z)-1c is reported. Both E- and Z-isomers are differentiated by
GC, MS data for both isomers are reported.
IR (neat): νmax 3034, 3001, 2934, 2833, 1651, 1639, 1606, 1573, 1509, 1454, 1399, 1301, 1284, 1269,
1240, 1177, 1150, 1092, 1032, 935 cm–1.
(E)-1-Methoxy-4-(2-methoxyethenyl)benzene ((E)-1c)4

1
H NMR (CDCl3, 400 MHz): δ 7.15 (d, J = 8.7 Hz, 2H), 6.92 (d, J = 13.0 Hz, 1H), 6.856.79 (m, 2H), 5.77
(d, J = 13.0 Hz, 1H), 3.78 (s, 3H), 3.65 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 158.0, 147.6, 129.0, 126.3 (2C), 114.2 (2C), 104.7, 56.6, 55.3.
MS (EI, 70 eV): m/z (relative intensity) = 164 (M+•, 100), 149 (67), 121 (99), 91 (18), 78 (15), 77 (26).
(Z)-1-Methoxy-4-(2-methoxyethenyl)benzene ((Z)-1c)4

1
H NMR (CDCl3, 400 MHz): δ 7.51 (d, J = 8.1 Hz, 2H), 6.856.82 (m, 2H), 6.04 (d, J = 7.0 Hz, 1H), 5.17
(d, J = 7.0 Hz, 1H), 3.78 (s, 3H), 3.74 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 157.7, 146.5, 129.5 (2C), 128.9, 113.7 (2C), 105.3, 60.6, 55.4.
S-6
1-Methoxy-3-(2-methoxyethenyl)benzene (1d)
Compound 1d was synthesized from m-anisaldehyde (0.426 mL, 3.50 mmol) according to procedure
A. Purification by flash column chromatography (PE/Et2O = 95:5) afforded 1d (235 mg, 1.43 mmol,
41%) as a clear oil and as a mixture of (E)-1d and (Z)-1d in a ratio E/Z = 52:48. As the two sets of
signals in the 1H and 13C NMR spectra are differentiated, an independent description for (E)-1d and
(Z)-1d is reported. Both E- and Z-isomers are separated by GC, MS data for both isomers are
reported.
IR (neat): νmax 3000, 2936, 2833, 1640, 1598, 1575, 1485, 1454, 1428, 1255, 1218, 1147, 1122, 1096,
1043, 994, 934 cm–1.
HRMS: calcd for C10H13O2 (M+H)+ : 165.0910 , found : 165.0909.
(E)-1-Methoxy-3-(2-methoxyethenyl)benzene ((E)-1d)

1
H NMR (CDCl3, 400 MHz): δ 7.18 (m, 1H), 7.07 (d, J = 13.0 Hz, 1H), 6.84 (m, 1H), 6.78 (m, 1H), 6.72
(m, 1H), 5.80 (d, J = 13.0 Hz, 1H), 3.81 (s, 3H), 3.69 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 159.9, 149.2, 137.9, 129.6, 117.7, 111.1, 110.8, 105.0, 56.5, 55.1.
(Z)-1-Methoxy-3-(2-methoxyethenyl)benzene ((Z)-1d)

1
H NMR (CDCl3, 400 MHz): δ 7.23‒7.21 (m, 2H), 7.13 (dt, J = 7.7, 1.3 Hz, 1H) 6.72 (m, 1H), 6.15 (d, J =
7.0 Hz, 1H), 5.21 (d, J = 7.0 Hz, 1H), 3.81 (s, 3H), 3.79 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 159.5, 148.3, 137.3, 129.1, 121.0, 113.7, 111.5, 105.6, 60.7, 55.1.
S-7
1-Methoxy-2-(2-methoxyethenyl)benzene (1e)
Compound 1e was synthesized from o-anisaldehyde (0.477 mg, 3.50 mmol) according to procedure
A. Purification by flash column chromatography (PE/Et2O = 99:1) afforded 1e (180 mg, 1.10 mmol,
31%) as a clear oil and as a mixture of (E)-1e and (Z)-1e in a ratio E/Z = 55:45. As the two sets of
signals in the 1H and 13C NMR spectra are differentiated, an independent description for (E)-1e and
(Z)-1e is reported. Both E- and Z-isomers are not differentied by GC, the same MS data for both
isomers is reported.
IR (neat): νmax 3000, 2933, 2833, 1649, 1637, 1597, 1576, 1488, 1461, 1434, 1269, 1237, 1153, 1116,
1088, 1053, 1028, 980, 936 cm–1.
HRMS: calcd for C10H12O2Na (M+Na)+ : 187.0730, found : 187.0731.
(E)-1-Methoxy-2-(2-methoxyethenyl)benzene ((E)-1e)

1
H NMR (CDCl3, 400 MHz): δ 7.28 (dd, J = 7.6, 1.7 Hz, 1H), 7.19‒7.14 (m, 2H), 6.92 (m, 1H), 6.86 (m,
1H), 6.07 (d, J = 13.0 Hz, 1H), 3.87 (s, 3H), 3.73 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 156.0, 149.7, 126.7, 126.1, 125.3, 120.8, 110.8, 100.6, 56.4, 55.4.
(Z)-1-Methoxy-2-(2-methoxyethenyl)benzene ((Z)-1e)

1
H NMR (CDCl3, 400 MHz): δ 8.03 (dd, J = 7.8, 1.6 Hz, 1H), 7.16 (m, 1H), 6.96 (m, 1H), 6.87 (m, 1H),
6.21 (d, J = 7.2 Hz, 1H), 5.68 (d, J = 7.2 Hz, 1H), 3.85 (s, 3H), 3.78 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 155.7, 147.9, 129.8, 126.9, 124.7, 120.5, 110.3, 98.8, 60.6, 55.6.
S-8
1,2-Dimethoxy-4-(2-methoxyethenyl)benzene (1f)
Compound 1f was synthesized from veratraldehyde (0.779 mg, 4.64 mmol) according to procedure A.
Purification by flash column chromatography (PE/Et2O = 80:20 then 50:50) afforded 1f (879 mg, 4.53
mmol, 98%) as a clear oil and as a mixture of (E)-1f and (Z)-1f in a ratio E/Z = 50:50. As the two sets of
signals in the 1H and 13C NMR spectra are differentiated, an independent description for (E)-1f and
(Z)-1f is reported. Both E- and Z-isomers are differentiated by GC, MS data for both isomers are
reported.
IR (neat): νmax 2935, 2834, 1643, 1590, 1514, 1463, 1259, 1235, 1155, 1139, 1120, 1026, 912 cm–1.
HRMS: calcd for C11H15O3 (M+H)+ : 195.1016, found : 195.1017.
(E)-1,2-Dimethoxy-4-(2-methoxyethenyl)benzene ((E)-1f)

1
H NMR (CDCl3, 400 MHz): δ 6.94 (d, J = 13.0 Hz, 1H), 6.76‒6.75 (m, 3H), 5.76 (d, J = 12.9 Hz, 1H),
3.86 (s, 3H), 3.84 (s, 3H), 3.65 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 149.1, 147.8, 147.4, 129.4, 117.6, 111.6, 111.0, 104.9, 56.5, 55.9, 55.7.
MS (EI, 70 eV): m/z (relative intensity) = 194 (M+•, 100), 179 (62), 151 (32), 119 (12), 91 (33), 77 (12),
65 (11).
(Z)-1,2-Dimethoxy-4-(2-methoxyethenyl)benzene ((Z)-1f)

1
H NMR (CDCl3, 400 MHz): δ 7.24 (d, J = 2.0 Hz, 1H), 7.06 (dd, J = 8.3, 2.0 Hz, 1H), 6.78 (d, J = 8.4 Hz,
1H), 6.04 (d, J = 7.0 Hz, 1H), 5.15 (d, J = 7.0 Hz, 1H), 3.87 (s, 3H), 3.84 (s, 3H), 3.74 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 148.5, 147.2, 146.6, 129.1, 120.8, 111.6, 108.3, 105.5, 60.6, 55.83,
55.77.
65 (12).
S-9
4-(2-Methoxyethenyl)-N,N-dimethylaniline (1g)
(E)-4-(2-Methoxyethenyl)-N,N-dimethylaniline ((E)-1g)4
Compound (E)-1g was synthesized from 4-dimethylaminobenzaldehyde (522.2 mg, 3.5 mmol)
according to procedure B. Purification by flash column chromatography (PE/Et2O = 80:20) afforded
(E)-1g (230.1 mg, 1.298 mmol, 47% over two steps) as a clear oil.
Formula: C11H15NO MW = 177.24 g.mol–1
IR (neat) : νmax 3033, 2333, 2892, 2830, 2798, 1640, 1613, 1520, 1347, 1241, 1198, 1151, 1117, 934,
817 cm–1.
1
H NMR (CDCl3, 400 MHz): δ 7.157.11 (m, 2H), 6.90 (d, J = 13.0 Hz, 1H), 6.706.67 (m, 2H), 5.78 (d, J
= 13.0 Hz, 1H), 3.66 (s, 3H), 2.93 (s, 6H).
13
C NMR (CDCl3, 100 MHz): δ 149.2, 146.6, 126.1 (2C), 125.0, 113.3 (2C), 105.2, 55.6, 40.9 (2C).
(Z)-4-(2-Methoxyethenyl)-N,N-dimethylaniline ((Z)-1g)4
Compound 1g was synthesized from 4-dimethylaminobenzaldehyde (754 mg, 5.00 mmol) according
to procedure A. Purification by flash column chromatography (PE/Et2O = 98:2 then 95:5 with 0.5%
v/v Et3N) afforded 1g (878 mg, 4.95 mmol, 99%) as a clear oil and as a mixture of (E)-1g and (Z)-1g in
a ratio E/Z = 40:60.

IR (neat): νmax 2932, 2826, 2797, 1651, 1640, 1608, 1519, 1445, 1397, 1348, 1328, 1267, 1239, 1197,
1190, 1162, 1151, 1117, 1091, 980, 945 cm–1.
The description of (Z)-1g from the mixture is reported.

1
H NMR (C6D6, 400 MHz): δ 7.807.76 (m, 2H), 6.686.65 (m, 2H), 5.75 (d, J = 7.0 Hz, 1H), 5.29 (d, J =
7.0 Hz, 1H), 3.21 (s, 3H), 2.52 (s, 6H).
13
C NMR (C6D6, 100 MHz): δ 149.2, 145.3, 129.9 (2C), 125.7, 112.8 (2C), 106.7, 59.9, 40.3 (2C).
S-10
3-Methoxy-4-(2-methoxyethenyl)-N,N-diethylaniline (1h)
Compound 1h was synthesized from 4-(diethylamino)-2-methoxybenzaldehyde (0.518 mg, 2.50

mmol) according to procedure A. Purification by flash column chromatography (PE/Et2O = 95:5 then
90:10) afforded 1h (523 mg, 2.22 mmol, 89%) as a clear oil and as a mixture of (E)-1h and (Z)-1h in a
ratio E/Z = 43:57. As the two sets of signals in the 1H and 13C NMR spectra are differentiated, an
independent description for (E)-1h and (Z)-1h is reported. Both E- and Z-isomers are differentiated by
IR (neat): νmax 2968, 2931, 2828, 1638, 1609, 1555, 1510, 1450, 1397, 1374, 1355, 1276, 1259, 1219,
1195, 1115, 1090, 1035, 1018, 980, 933 cm–1.
HRMS: calcd for C14H22NO2 (M+H)+ : 236.1645, found : 236.1643.
(E)-3-Methoxy-4-(2-methoxyethenyl)-N,N-diethylaniline ((E)-1h)
Formula: C14H21NO2 MW = 235.32 g.mol–1

1
H NMR (CDCl3, 400 MHz): δ 7.11 (d, J = 8.4 Hz, 1H), 7.01 (d, J = 13.0 Hz, 1H), 6.28 (dd, J = 8.5, 2.5 Hz,
1H), 6.24 (dd, J =10.6, 2.4 Hz, 1H), 5.98 (d, J = 13.0 Hz, 1H), 3.86 (s, 3H), 3.69 (s, 3H), 3.37 (q, J = 7.1
Hz, 4H), 1.19 (t, J = 7.1 Hz, 6H).
13
C NMR (CDCl3, 100 MHz): δ 157.2, 147.5, 146.9, 127.1, 113.0, 101.0, 96.1, 95.4, 56.3, 55.4, 44.64
(2C), 12.7 (2C).
(Z)-3-Methoxy-4-(2-methoxyethenyl)-N,N-diethylaniline ((Z)-1h)
Formula: C14H21NO2 MW = 235.32 g.mol–1

1
H NMR (CDCl3, 400 MHz): δ 7.88 (d, J = 8.7 Hz, 1H), 6.32 (dd, J = 8.7, 2.5 Hz, 1H), 6.24 (dd, J = 10.6,
2.4 Hz, 1H), 6.04 (d, J = 7.1 Hz, 1H), 5.57 (d, J = 7.1 Hz, 1H), 3.84 (s, 3H), 3.73 (s, 3H), 3.37 (q, J = 7.1
Hz, 4H), 1.19 (t, J = 7.1 Hz, 6H).
13
C NMR (CDCl3, 100 MHz): δ 157.0, 147.4, 145.0, 130.5, 112.8, 104.9, 104.6, 99.2, 60.2, 55.6, 44.60
(2C), 12.8 (2C).
S-11
3-(2-Methoxyethenyl)pyridine (1i)
Compound 1i was synthesized from 3-pyridinecarboxaldehyde (0.479 mL, 5.00 mmol) according to
procedure A. Purification by flash column chromatography (PE/EtOAc = 6:4 then 1:1) afforded 1i (647
mg,, 4.79 mmol, 96%) as an orange oil and as a mixture of (E)-1i and (Z)-1i in a ratio E/Z = 61:39. As
the two sets of signals in the 1H and 13C NMR spectra are differentiated, an independent description
for (E)-1i and (Z)-1i is reported. Both E- and Z-isomers are not differentiated by GC, the same MS data
for both isomers is reported.
IR (neat): νmax 3028, 2936, 2834, 1651, 1639, 1566, 1478, 1455, 1416, 1337, 1283, 1244, 1207, 1151,
1123, 1093, 1042, 1023, 986, 935 cm–1.
MS (EI, 70 eV): m/z (relative intensity) = 135 (M+•, 100), 120 (43), 92 (47), 65 (43).
(E)-3-(2-Methoxyethenyl)pyridine ((E)-1i)5

1
H NMR (CDCl3, 400 MHz): δ 8.48 (d, J = 2.1 Hz, 1H), 8.35 (dd, J = 4.9, 1.5 Hz, 1H), 7.53 (m, 1H), 7.18
(m, 1H), 7.08 (d, J = 13.1 Hz, 1H), 5.75 (d, J = 13.1 Hz, 1H), 3.72 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 150.2, 147.2, 147.0, 132.4, 131.6, 123.5, 101.5, 56.7.
(Z)-3-(2-Methoxyethenyl)pyridine ((Z)-1i)5

1
H NMR (CDCl3, 400 MHz): δ 8.67 (d, J = 1.9 Hz, 1H), 8.36 (dd, J = 4.9, 1.5 Hz, 1H), 7.97 (dt, J = 8.0, 1.9
Hz, 1H), 7.18 (m, 1H), 6.25 (d, J = 6.9 Hz, 1H), 5.20 (d, J = 6.9 Hz, 1H), 3.81 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 149.9, 149.5, 146.7, 135.0, 132.0, 123.2, 102.2, 61.0.
5
Lam, R.H.; Walker, D.B.; Tucker, M.H.; Gatus, M.R.D.; Bhadbhade, M.; Messerle, B. A. et al.
Organometallics, 2015, 34, 43124317.
S-12
3-(2-Methoxyethenyl)-1-methyl-1H-indole (1j)
Compound 1j was synthesized from 1-methylindole-3-carboxaldehyde (821 mg, 5.00 mmol)

according to procedure A. Purification by flash column chromatography (PE/Et2O = 100:0 then 98:2
then 95:5 and then 90:10 with 0.5% v/v Et3N) afforded 1j (910 mg, 4.86 mmol, 97%) as an orange oil
and as a mixture of (E)-1j and (Z)-1j in a ratio E/Z = 36:64. As the two sets of signals in the 1H and 13C
NMR spectra are differentiated, an independent description for (E)-1j and (Z)-1j is reported. Both E-
and Z-isomers are differentiated by GC, MS data for both isomers are reported.
IR (neat): νmax 3046, 2932, 2830, 1651, 1612, 1533, 1475, 1403, 1376, 1331, 1318, 1268, 1238, 1215,
1142, 1093, 1014, 973, 923 cm–1.
(E)-3-(2-Methoxyethenyl)-1-methyl-1H-indole ((E)-1j)6

1
H NMR (C6D6, 400 MHz): δ 7.85 (m, 1H), 7.337.25 (m, 2H), 7.22 (d, J = 12.9 Hz, 1H), 7.07 (m, 1H),
6.48 (s, 1H), 6.14 (d, J = 13.0 Hz, 1H), 3.40 (s, 3H), 2.95 (s, 3H).
13
C NMR (C6D6, 100 MHz): δ 147.1, 137.9, 127.1, 125.3, 122.0, 120.3, 119.6, 111.5, 109.6, 98.2, 56.0,
31.8.
MS (EI, 70 eV): m/z (relative intensity) = 187 (M+•, 100), 172 (65), 144 (98), 128 (12), 115 (17), 77
(16).
(Z)-3-(2-Methoxyethenyl)-1-methyl-1H-indole ((Z)-1j)6

1
H NMR (C6D6, 400 MHz): δ 7.85 (m, 1H), 7.62 (s, 1H), 7.337.25 (m, 2H), 7.07 (m, 1H), 5.93 (d, J = 6.5
Hz, 1H), 5.80 (d, J = 6.5 Hz, 1H), 3.35 (s, 3H), 3.02 (s, 3H).
13
C NMR (C6D6, 100 MHz): δ 144.6, 136.8, 129.0, 128.0, 121.9, 119.5, 119.2, 110.7, 109.5, 97.9, 59.7,
32.0.
(15).
6
Shimasaki, T.; Konno, Y.; Tobisu, M.; Chatani, N. et al. Org. Lett. 2009, 11, 48904892.
S-13
2-(2-Methoxyethenyl)-1-methyl-1H-pyrrole (1k)
Compound 1k was synthesized from N-methylpyrrole-2-carboxaldehyde (557 mg, 5.00 mmol)

according to procedure A. Purification by flash column chromatography (PE/Et2O = 98:2 then 95:5
with 0.5% v/v Et3N) afforded 1k (615 mg, 4.48 mmol, 90%) as a dark red oil and as a mixture of (E)-1k
and (Z)-1k in a ratio E/Z = 38:62. As the two sets of signals in the 1H and 13C NMR spectra are
differentiated, an independent description for (E)-1k and (Z)-1k is reported. Both E- and Z-isomers
are differentiated by GC, MS data for both isomers are reported.
IR (neat): νmax 3100, 2935, 2830, 1651, 1486, 1457, 1302, 1273, 1238, 1217, 1127, 1096, 1057, 1003,
982, 935 cm–1.
HRMS: calcd for C8H12ON (M+H)+ : 138.0913, found : 138.0910.
(E)-2-(2-Methoxyethenyl)-1-methyl-1H-pyrrole ((E)-1k)

1
H NMR (C6D6, 400 MHz): δ 6.79 (d, J = 12.7 Hz, 1H), 6.32 (m, 1H), 6.266.23 (m, 2H), 5.56 (d, J = 12.7
Hz, 1H), 3.18 (s, 3H), 2.88 (s, 3H).
13
C NMR (C6D6, 100 MHz): δ 148.7, 129.5, 121.8, 108.0, 104.8, 96.0, 56.4, 33.24.
(Z)-2-(2-Methoxyethenyl)-1-methyl-1H-pyrrole ((Z)-1k)

1
H NMR (C6D6, 400 MHz): δ 7.06 (dd, J = 3.6, 1.7 Hz, 1H), 6.376.35 (m, 2H), 5.72 (d, J = 6.9 Hz, 1H),
5.05 (d, J = 6.9 Hz, 1H), 3.21 (s, 3H), 2.92 (s, 3H).
13
C NMR (C6D6, 100 MHz): δ 144.6, 128.6, 121.1, 110.8, 108.2, 95.8, 59.8, 33.19.
S-14
3-(2-Methoxyethenyl)furan (1l)
Compound 1l was synthesized from furan-3-carboxaldehyde (0.446 mL, 5.00 mmol) according to
procedure A. Purification by flash column chromatography (PE/Et2O = 100:0 then 98:2 with 0.5% v/v
Et3N) afforded 1l (353 mg, 2.84 mmol, 57%) as an orange oil and as a mixture of (E)-1l and (Z)-1l in a
ratio E/Z = 62:38 contaminated by (O)PPh3. As the two sets of signals in the 1H and 13C NMR spectra
are differentiated, an independent description for (E)-1l and (Z)-1l is reported.
IR (neat): νmax 3005, 2935, 2833, 1656, 1573, 1505, 1438, 1336, 1270, 1237, 1202, 1161, 1141, 1127,
1101, 1066, 1025, 931 cm–1.
(E)-3-(2-Methoxyethenyl)furan ((E)-1l)7

1
H NMR (C6D6, 400 MHz): δ 7.10 (m, 1H), 7.06 (m, 1H), 6.74 (d, J = 13.0 Hz, 1H), 6.15 (m, 1H), 5.47 (d,
J = 13.0 Hz, 1H), 3.15 (s, 3H).
13
C NMR (C6D6, 100 MHz): δ 148.7, 143.4, 138.5, 122.0, 107.7, 95.2, 55.8.
(Z)-3-(2-Methoxyethenyl)furan ((Z)-1l)7

1
H NMR (C6D6, 400 MHz): δ 7.69 (m, 1H), 7.14 (m, 1H), 6.58 (m, 1H), 5.65 (d, J = 6.5 Hz, 1H), 5.05 (d, J
= 6.5 Hz, 1H), 3.09 (s, 3H).
13
C NMR (C6D6, 100 MHz): δ 147.0, 142.4, 141.0, 120.9, 111.3, 96.9, 59.7.
7
Tofi, M.; Georgiou, T.; Montagnon, T.; Vassilikogiannakis, G. Org. Lett. 2005, 7, 33473350.
S-15
3-(2-Methoxyethenyl)thiophene (1m)
Compound 1m was synthesized from 3-thiophenecarboxaldehyde (572 mg, 5.00 mmol) according to
procedure A. Purification by flash column chromatography (PE/Et2O = 100:0 then 98:2 with 0.5% v/v
Et3N) afforded 1m (625 mg, 4.46 mmol, 89%) as a pale yellow oil and as a mixture of (E)-1m and (Z)-
1m in a ratio E/Z = 61:39. As the two sets of signals in the 1H and 13C NMR spectra are differentiated,
an independent description for (E)-1m and (Z)-1m is reported. Both E- and Z-isomers are
differentiated by GC, MS data for both isomers are reported.
IR (neat): νmax 3099, 2932, 2833, 1642, 1452, 1414, 1386, 1332, 1271, 1216, 1140, 1119, 1095, 995,
931 cm–1.
(E)-3-(2-Methoxyethenyl)thiophene ((E)-1m)8
Formula: C7H8OS MW = 140.20 g.mol–1

1
H NMR (C6D6, 400 MHz): δ 6.92 (dd, J = 5.0, 3.0 Hz, 1H), 6.86 (d, J = 13.0 Hz, 1H), 6.80 (dd, J = 5.0, 1.3
Hz, 1H), 6.61 (m, 1H), 5.69 (d, J = 13.0 Hz, 1H), 3.14 (s, 3H).
13
C NMR (C6D6, 100 MHz): δ 149.3, 137.9, 125.9, 124.9, 118.2, 100.5, 55.8.
(Z)-3-(2-Methoxyethenyl)thiophene ((Z)-1m)8
Formula: C7H8OS MW = 140.20 g.mol–1

1
H NMR (C6D6, 400 MHz): δ 7.36 (m, 1H), 7.31 (dd, J = 5.0, 1.2 Hz, 1H), 6.87 (m, 1H), 5.64 (d, J = 6.7
Hz, 1H), 5.26 (d, J = 6.7 Hz, 1H), 3.10 (s, 3H).
13
C NMR (C6D6, 100 MHz): δ 146.7, 137.0, 128.9, 124.5, 121.9, 101.2, 59.8.
8
Masataka, K.; Takuya, K.; Fumitoshi, K. J. Am. Chem. Soc. 2011, 133, 3234.
S-16
1-Methoxyundec-1-ene (1n)
Compound 1n was synthesized from decanal (0.961 mL, 5.00 mmol) according to procedure A.
Purification by flash column chromatography (PE 100%) afforded 1n (695 mg, 3.77 mmol, 75%) as a
clear oil and as a mixture of (E)-1n and (Z)-1n in a ratio E/Z = 51:49. As the two sets of signals in the
1
H NMR spectrum are differentiated, an independent description for (E)-1n and (Z)-1n is reported.
Both E- and Z-isomers are differentiated by GC, MS data for both isomers are reported.
IR (neat): νmax 3034, 2997, 2955, 2923, 2853, 1656, 1462, 1390, 1260, 1209, 1109, 932 cm–1.
The 13C NMR signals for (E)- and (Z)-isomers could not be differentiated:
13
C NMR (CDCl3, 100 MHz): δ 147.0, 146.0, 107.4, 103.4, 59.6, 56.0, 32.1 (2C), 31.0, 30.0, 29.8, 29.7
(2C), 29.50 (2C), 29.45, 29.2, 27.8, 24.0, 22.8 (2C), 14.3 (2C).
(E)-1-Methoxyundec-1-ene ((E)-1n)9
1
H NMR (CDCl3, 400 MHz): δ 6.27 (d, J = 12.6 Hz, 1H), 4.73 (dt, J = 12.6, 7.3 Hz, 1H), 3.57 (s, 3H),
1.931.88 (m, 2H), 1.451.15 (m, 14H), 0.89 (br t, J = 6.3 Hz, 3H).
(Z)-1-Methoxyundec-1-ene ((Z)-1n)9
1
H NMR (CDCl3, 400 MHz): δ 5.86 (dt, J = 6.2, 1.4 Hz, 1H), 4.33 (m, 1H), 3.50 (s, 3H), 2.072.02 (m,
2H), 1.451.15 (m, 14H), 0.88 (br t, J = 6.3 Hz, 3H).
2-(2-Methoxyethenyl)naphthalene (1o)
Compound 1o was synthesized from 2-naphthaldehyde (1593 mg, 10 mmol) according to procedure
A. Purification by flash column chromatography (PE/Et2O = 100:0 and 98:2) afforded 1o (1580 mg,
8.576 mmol, 86%) as a clear oil and as a mixture of (E)-1o and (Z)-1o in a ratio E/Z = 57:43. As the two
sets of signals in the 1H and 13C NMR spectra are differentiated, an independent description for (E)-1o
and (Z)-1o is reported. Both E- and Z-isomers are differentiated by GC, MS data for both isomers are
reported.
IR (neat): νmax 3054, 3012, 2933, 2831, 1639, 1625, 1597, 1505, 1330, 1281, 1269, 1257, 1225, 1204,
1154, 1125, 1089, 933, 856, 820 cm–1.
9
Guella, G.; Mancini, I; Pietra, F. Helv. Chim. Acta 1987, 70, 14001411.
S-17
(E)-2-(2-Methoxyethenyl)naphthalene ((E)-1o)10
Formula: C13H12O Mw = 184.23 g.mol–1

1
H NMR (CDCl3, 400 MHz): δ 7.787.71 (m, 3H), 7.58 (s, 1H), 7.437.39 (m, 3H), 7.18 (d, J = 13.0 Hz,
1H), 5.97 (d, J = 13.0 Hz, 1H), 3.72 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 149.4, 134.1, 134.0, 132.1, 128.3, 127.8, 127.5, 126.3, 125.1, 123.8,
123.4, 105.4, 56.8.
(Z)-2-(2-Methoxyethenyl)naphthalene ((Z)-1o)10
Formula: C13H12O Mw = 184.23 g.mol–1

1
H NMR (CDCl3, 400 MHz): δ 8.00 (s, 1H), 7.787.71 (m, 4H), 7.437.39 (m, 2H), 6.21 (d, J = 7.0 Hz,
1H), 5.36 (d, J = 7.0 Hz, 1H), 3.82 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 148.5, 133.8, 133.7, 132.0, 128.0, 127.7, 127.6, 127.2, 126.6, 125.9,
125.3, 105.9, 60.9.
(E)-1,2,3-Trimethoxy-5-(2-methoxyethenyl)benzene ((E)-1p)11
Compound (E)-1p was synthesized from 3,4,5-trimethoxybenzaldehyde (490.5 mg, 2.5 mmol)
according to procedure B. Purification by flash column chromatography (PE/Et2O = 80:20) afforded
(E)-1p (135 mg, 0.60 mmol, 29% over two steps) as a colorless oil.
IR (neat) : νmax 2936, 2834, 1641, 1578, 1508, 1452, 1415, 1326, 1242, 1213, 1185, 1159, 1120, 1006,
933 cm–1.
1
H NMR (CDCl3, 400 MHz): δ 6.98 (d, J = 12.9 Hz, 1H), 6.44 (s, 2H), 5.76 (d, J = 12.9 Hz, 1H), 3.86 (s,
6H), 3.82 (s, 3H), 3.68 (s, 3H).
10
Guo, L.; Leiendecker, M.; Hsiao, C.; Baumann, C.; Rueping, M. Chem. Commun. 2015, 51, 19371940.
11
Gemma, S.; Brogi, S.; Patil, P. R.; Giovani, S.; Lamponi, S.; Cappelli, A.; Novellino, E.; Brown, A.; Higgins, M.K.;
Mustafa, K.; Szestak, T.; Craig, A. G.; Campiani, G.; Butini, S.; Brindisi, M. RSC Advances 2014, 4, 4969 –4781.
S-18
13
C NMR (CDCl3, 100 MHz): δ 153.5 (2C), 148.8, 136.5, 132.3, 105.3, 102.4 (2C), 61.1, 56.7, 56.2 (2C).
(14), 95 (11).
2. Nickel-catalyzed Kumada coupling of alkenyl methyl ethers

General procedure C
A 10 mL oven-dried pressure vial, equipped with a rubber septum, was charged with alkenyl methyl
ether (1 equiv). The vial was put under vacuum and backfilled with argon (3 times), then nickel(II)
acetate (0.025 equiv) and triphenylphosphine oxide (0.1 equiv) were added. The vial was put under
vacuum and backfilled with argon (3 times), and toluene was added with a syringe to have a
concentration of 0.3 M in alkenyl methyl ether. The Grignard reagent (1.5 equiv) was then added
dropwise with a syringe at rt over 5 min and the vial was sealed with a Teflon cap. After 24 h at 40 °C,
the reaction mixture was quenched with an aqueous saturated solution of NH4Cl and diluted with
EtOAc. Both layers were separated and the aqueous phase was extracted with EtOAc (3 times). The
combined organic extracts were washed with H2O and brine, dried over anhydrous Na2SO4, filtered
and concentrated under reduced pressure. The residue was purified by flash column chromatography
on silica gel, using a mixture of PE (or pentane)/Et2O (or EtOAc) as the eluent, to afford the desired
product. All the yields indicated in this section are isolated yields, unless otherwise specified. In the
case where the expected compound could not be separated from the side products, the yield was
determined by 1H NMR using 1,3,5-trimethoxybenzene as the internal standard.
General procedure D
A 10 mL oven-dried pressure vial, equipped with a rubber septum, was charged with (E)-alkenyl
methyl ether (E)-1a, (E)-1c, (E)-1f, (E)-1g or (E)-1p (1 equiv). The vial was put under vacuum and
backfilled with argon (3 times), then nickel(II) acetate (0.025 equiv) and triphenylphosphine oxide
(0.1 equiv) were added. The vial was put under vacuum and backfilled with argon (3 times), and
toluene was added with a syringe to have a concentration of 0.3 M in (E)-alkenyl methyl ether. The
Grignard reagent (3 equiv) was then added dropwise with a syringe at rt over 5 min, the vial was
sealed with a Teflon cap. After 5 h to 27 h at 40 °C, the reaction mixture was quenched with an
aqueous saturated solution of NH4Cl and diluted with Et2O. Both layers were separated and the
aqueous phase was extracted with Et2O (3 times). The combined organic extracts were washed with
H2O and brine, dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The
residue was purified by flash column chromatography on silica gel, using a mixture of PE (or
pentane)/Et2O as the eluent, to afford the desired product. All yields indicated in this section are
isolated yields, unless otherwise specified. The products (E)-3c, (E)-3f, (E)-6a and (E)-6b will be
described from the corresponding E/Z mixtures obtained by procedure C.
S-19
(E)-1-Methyl-4-(2-phenylethenyl)benzene ((E)-3a)12
Formula: C15H14 MW = 194.27 g.mol–1
Compound (E)-3a was synthesized from (E)-(2-methoxyethenyl)benzene (E)-1a (69.3 mg, 3.77 mmol)
and p-tolylmagnesium bromide 2 (0.816 mL, 0.76 mmol, 0.95 M in THF) according to procedure C.
Purification by flash column chromatography (PE 100%) afforded (E)-3a (73.7 mg, 0.38 mmol, 73%
NMR yield) as a white solid, contaminated with 1,4-diphenylbuta-1,3-diene (15% w/w).
mp = 110–112 °C.
IR (solid state): νmax 3021, 2915, 1593, 1510, 1493, 1448, 1304, 969 cm–1.
1
H NMR (CDCl3, 400 MHz): δ 7.517.48 (m, 2H), 7.447.39 (m, 2H), 7.367.30 (m, 2H), 7.23 (m, 1H),
7.16 (d, J = 7.9 Hz, 2H), 7.09 (d, JAB = 16.4 Hz, 1H), 7.04 (d, JAB = 16.4 Hz, 1H), 2.35 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 137.7 (2C), 134.7, 129.5 (2C), 128.79 (2C), 128.76, 127.8, 127.5, 126.6
(2C), 126.5 (2C), 21.4.
(13), 96 (18), 89 (15).
(Z)-1-Methyl-4-(2-phenylethenyl)benzene ((Z)-3a)13
Compound (Z)-3a was synthesized from (Z)-(2-methoxyethenyl)benzene (Z)-1a (74.6 mg, 0.56 mmol)
and p-tolylmagnesium bromide 2 (0.878 mL, 0.83 mmol, 0.95 M in THF) according to procedure C.
Purification by flash column chromatography (PE 100%) afforded (Z)-3a (84.1 mg, 0.43 mmol, 78%
NMR yield) as a clear oil, contaminated with 4,4’-dimethyl-1,1’-biphenyl (18% w/w).
IR (neat): νmax 3023, 2918, 1502, 1447, 1114, 1029, 1006, 919 cm–1.
1
H NMR (CDCl3, 400 MHz): δ 7.277.12 (m, 7H), 7.037.00 (m, 2H), 6.55 (sapp, 2H), 2.30 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 137.6, 137.0, 134.4, 130.3, 129.7, 129.0 (2C), 128.98 (2C), 128.93 (2C),
128.3 (2C), 127.1, 21.4.
(12), 152 (11), 115 (15), 96 (20), 89 (18).
12
Guastavino, J. F.; Budén, M. E.; Rossi, R. A. J. Org. Chem. 2014, 79, 9104–9111.
13
Liu, Y.; Hu, L.; Chen, H.; Du, H. Chem. Eur. J. 2015, 21, 3495–3501.
S-20
(1E,3E)-1,4-Diphenylbuta-1,3-diene (4)14
Formula: C16H14 Mw = 206.28 g.mol–1
Compound 4 could be isolated as a pure compound as a white solid from the reaction of
(2-methoxyethenyl)benzene 1a with p-tolylmagnesium bromide 2.
mp = 145–147 °C
IR (solid state): νmax 3057, 3016, 2924, 2853, 1491, 1444, 1073, 991, 984, 738, 690 cm –1.
1
H NMR (CDCl3, 400 MHz): δ 7.457.43 (m, 4H), 7.357.31 (m, 4H), 7.257.21 (m, 2H), 6.996.92 (m,
2H), 6.716.64 (m, 2H).
13
C NMR (CDCl3, 100 MHz): δ 137.5 (2C), 133.0 (2C), 129.4 (2C), 128.8 (4C), 127.7 (2C), 126.5 (4C).
(17), 101 (15), 91 (82), 89 (23).
1-(Benzyloxy)-4-[2-(4-methylphenyl)ethenyl]benzene (3b)
Compound 3b was synthesized from 1-(benzyloxy)-4-(2-methoxyethenyl)benzene 1b (240.3 mg, 1.0

mmol) and p-tolylmagnesium bromide 2 (2.027 mL, 1.5 mmol, 0.74 M in THF) according to procedure
C. Purification by flash column chromatography (PE/Et2O = 100:0 and 90:10) afforded 3b (207.7 mg,
0.691 mmol, 69%) as a white solid and as a mixture of (E)-3b and (Z)-3b in a ratio E/Z = 39:61. The
(E)- and (Z)-isomers were partially separated by preparative thin layer chromatography (TLC)
(PE/Et2O = 100:0 and 9:1). The spectral data are given for each stereoisomer (E)-3b and (Z)-3b.
(E)-1-(Benzyloxy)-4-[2-(4-methylphenyl)ethenyl]benzene ((E)-3b)
Compound (E)-3b was isolated as a grey solid.
mp = 174–177 °C.
959 cm–1.
14
Hakim Siddiki, S. M. A.; Touchy, A. S.; Kon, K.; Shimizu, K.-I. Chem. Eur. J. 2016, 22, 61116119.
S-21
1
H NMR (CDCl3, 400 MHz): δ 7.467.31 (m, 9H), 7.16 (d, J = 7.9 Hz, 2H), 7.02 (d, JAB = 16.3 Hz, 1H),
6.996.95 (m, 2H), 6.95 (d, JAB = 16.3 Hz, 1H), 5.09 (s, 2H), 2.36 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 158.5, 137.2, 137.1, 135.0, 130.8, 129.5 (2C), 128.8 (2C), 128.1, 127.7
(2C), 127.6 (2C), 127.3, 126.9, 126.3 (2C), 115.2 (2C), 70.2, 21.4.
(21), 91 (97), 65 (11).
HRMS: calcd for C22H21O (M+H)+ : 301.1587, found : 301.1581.
(Z)-1-(Benzyloxy)-4-[2-(4-methylphenyl)ethenyl]benzene ((Z)-3b)
Compound (Z)-3b was isolated as a pale yellow solid.
mp = 75–76 °C.
IR (solid state): νmax 3011, 2920, 2864, 1604, 1573, 1507, 1454, 1381, 1299, 1244, 1175, 1111, 1021
cm–1.
1
H NMR (CDCl3, 400 MHz): δ 7.47–7.32 (m, 5H), 7.24–7.18 (m, 4H), 7.06 (d, J = 7.8 Hz, 2H), 6.88–6.83
(m, 2H), 6.50 (s, 2H), 5.06 (s, 2H), 2.34 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 158.0, 137.1, 136.8, 134.7, 130.3, 130.2 (2C), 129.2, 129.1 (2C), 129.0,
128.9 (2C), 128.7 (2C), 128.1, 127.6 (2C), 114.6 (2C), 70.1, 21.4.
91 (100), 65 (12).
HRMS: calcd for C22H20ONa (M+Na)+ : 323.1406, found : 323.1407.
1-Methoxy-4-[2-(4-methylphenyl)ethenyl]benzene (3c)
Compound 3c was synthesized from 1-methoxy-4-(2-methoxyethenyl)benzene 1c (163.9 mg, , 0.998

mmol) and p-tolylmagnesium bromide 2 (1.528 mL, 1.497 mmol, 0.95 M in THF) according to
procedure C. Purification by flash column chromatography (PE/Et2O = 100:0 then 99:1 then 98:2)
afforded 3c (160 mg, 0.713 mmol, 71%) as a white solid and as a mixture of (E)-3c and (Z)-3c in a ratio
independent description for (E)-3c and (Z)-3c is reported. Both E- and Z-isomers are differentiated by
IR (solid state): νmax 3008, 2957, 1606, 1514, 1265, 1251, 1177, 1034, 908 cm–1.
S-22
(E)-1-Methoxy-4-[2-(4-methylphenyl)ethenyl]benzene ((E)-3c)15

1
H NMR (CDCl3, 400 MHz): δ 7.457.41 (m, 2H), 7.38 (d, J = 8.1 Hz, 2H), 7.177.14 (m, 2H), 7.02 (d, JAB
= 16.7 Hz, 1H), 6.94 (d, JAB = 16.3 Hz, 1H), 6.906.87 (m, 2H), 3.82 (s, 3H), 2.35 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 159.3, 137.2, 135.0, 130.5, 129.5 (2C), 127.7 (2C), 127.4, 126.7, 126.3
(2C), 114.3 (2C), 55.5, 21.4.
(10).
(Z)-1-Methoxy-4-[2-(4-methylphenyl)ethenyl]benzene ((Z)-3c)16

1
H NMR (CDCl3, 400 MHz): δ 7.217.18 (m, 2H), 7.177.14 (m, 2H), 7.047.02 (m, 2H), 6.776.74 (m,
2H), 6.47 (sapp, 2H), 3.78 (s, 3H), 2.31 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 158.7, 136.8, 134.8, 130.2 (2C), 130.0, 129.2, 129.0 (2C), 128.9, 128.8
(2C), 113.7 (2C), 55.3, 21.4.
1-Methoxy-3-[2-(4-methylphenyl)ethenyl]benzene (3d)
Compound 3d was synthesized from 1-methoxy-3-(2-methoxyethenyl)benzene 1d (164.2 mg, 1.0

C. Purification by flash column chromatography (PE/Et2O = 100:0 and 90:10) afforded 3d (139.5 mg,
0.6219 mmol, 62%) as a clear oil and as a mixture of (E)-3d and (Z)-3d in a ratio E/Z = 56:44. The (E)-
and (Z)-isomers were separated by preparative TLC (PE/Et2O = 95:5). The spectral data are given for
each stereoisomer (E)-3d and (Z)-3d.
15
Puthiaraj, P.; Pitchumani, K. Green Chem. 2014, 16, 42234233.
16
Antonioletti, R.; Bonadies, F.; Ciammaichella, A.; Viglianti, A. Tetrahedron 2008, 64, 46444648.
S-23
(E)-1-Methoxy-3-[2-(4-methylphenyl)ethenyl]benzene ((E)-3d)17
Compound (E)-3d was isolated as a white solid.
mp = 7577 °C.
IR (neat): νmax 3000, 2919, 2800, 1601, 1577, 1485, 1434, 1269, 1256, 1151, 1051, 972 cm–1.
1
H NMR (CDCl3, 400 MHz): δ 7.41 (d, J = 8.1 Hz, 2H), 7.26 (m, 1H), 7.16 (d, J = 8.0 Hz, 2H), 7.11‒7.00
(m, 4H), 6.80 (ddd, J = 8.2, 2.6, 0.8 Hz, 1H), 3.84 (s, 3H), 2.35 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 160.0, 139.1, 137.7, 134.6, 129.7, 129.5 (2C), 129.1, 127.7, 126.6 (2C),
119.3, 113.2, 111.7, 55.4, 21.4.
(12), 89 (11).
(Z)-1-Methoxy-3-[2-(4-methylphenyl)ethenyl]benzene ((Z)-3d)17
Compound (Z)-3d was isolated as a clear oil.
IR (neat): νmax 3008, 2921, 2833, 1596, 1577, 1511, 1488, 1463, 1452, 1433, 1318, 1283, 1259, 1238,
1175, 1133, 1043 cm–1.
1
H NMR (CDCl3, 400 MHz): δ 7.19‒7.14 (m, 3H), 7.05 (d, J = 7.9 Hz, 2H), 6.87 (d, J = 7.6 Hz, 1H), 6.83
(m, 1H), 6.76 (dd, J = 8.2, 2.2 Hz, 1H), 6.59 (d, JAB = 12.2 Hz, 1H), 6.54 (d, JAB = 12.3 Hz, 1H), 3.69 (s,
3H), 2.32 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 159.5, 139.0, 137.0, 134.4, 130.6, 129.6, 129.3, 129.01 (2C), 128.96
(2C), 121.6, 113.9, 113.2, 55.2, 21.4.
(13), 89 (10).
17
Srinivas, P.; Srinivas, K.; Likhar, P.R.; Sridhar, B; Mohan, K.V.; Bhargava, S.; Kantam, M.L. J. Organomet. Chem.
2011, 696, 795‒801.
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1-Methoxy-2-[2-(4-methylphenyl)ethenyl]benzene (3e)
Compound 3e was synthesized from 1-methoxy-2-(2-methoxyethenyl)benzene 1e (150.6 mg, 0.9172

procedure C. Purification by flash column chromatography (PE/Et2O = 100:0 then 99:1) afforded 3e
(127.8 mg, 0.5696 mmol, 62%) as an oil and as a mixture of (E)-3e and (Z)-3e in a ratio E/Z = 61:39. As
the two sets of signals in the 1H and 13C NMR spectra are differentiated, an independent description
for (E)-3e and (Z)-3e is reported. Both E- and Z-isomers are differentiated by GC, MS data for both
isomers are reported.
IR (neat): νmax 3019, 2919, 2835, 1596, 1577, 1511, 1486, 1462, 1436, 1290, 1242, 1176, 1161, 1106,
1049, 1028, 970 cm–1.
HRMS: calcd for C16H16ONa (M+Na)+ : 247.1093 , found : 247.1092.
(E)-1-Methoxy-2-[2-(4-methylphenyl)ethenyl]benzene ((E)-3e)18

1
H NMR (CDCl3, 400 MHz): δ 7.58 (dd, J =7.7, 1.6 Hz, 1H), 7.46‒7.41 (m, 3H), 7.20 (m, 1H), 7.15‒7.11
(m, 2H), 7.08 (d, J JAB = 16.5 Hz, 1H), 6.95 (m, 1H), 6.89 (m, 1H), 3.86 (s, 3H), 2.34 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 156.9, 137.3, 135.3, 129.4 (2C), 129.2, 128.55, 126.7, 126.6 (2C), 126.4,
122.6, 120.9, 111.0, 55.61, 21.4.
89 (12).
(Z)-1-Methoxy-2-[2-(4-methylphenyl)ethenyl]benzene ((Z)-3e)

1
H NMR (CDCl3, 400 MHz): δ 7.24-7.17 (m, 2H), 7.15‒7.11 (m, 2H), 6.98 (d, J = 8.5 Hz, 2H), 6.86 (m,
1H), 6.75 (tdapp, J = 7.4, 0.7 Hz, 1H), 6.63 (d, JAB = 12.3 Hz, 1H), 6.58 (d, JAB = 12.3 Hz, 1H), 3.81 (s, 3H),
2.27 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 157.3, 136.8, 134.5, 130.3, 130.2, 128.89 (2C), 128.87 (2C), 128.6,
126.5, 125.1, 120.3, 110.8, 55.57, 21.3.
18
Schmidt, B.; Elizarov, N.; Berger, R.; Hölter, F. Org. Biomol. Chem. 2013, 11, 3674‒3691.
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89 (13).
1,2-Dimethoxy-4-[2-(4-methylphenyl)ethenyl]benzene (3f)
Compound 3f was synthesized from 1,2-dimethoxy-4-(2-methoxyethenyl)benzene 1f (194.2 mg, 1.0

C. Purification by flash column chromatography (PE/Et2O = 99:1 and 95:5) afforded 3f (183.6 mg,
0.7219 mmol, 72%) as a white solid and as a mixture of (E)-3f and (Z)-3f in a ratio E/Z = 53:47. The
(E)- and (Z)-isomers were separated by preparative TLC (PE/Et2O = 95:5). The spectral data are given
for each isomer (E)-3f and (Z)-3f.
(E)-1,2-Dimethoxy-4-[2-(4-methylphenyl)ethenyl]benzene ((E)-3f)19
Compound (E)-3f was isolated as a white solid.
mp = 117119 °C.
IR (neat): νmax 3004, 2918, 2845, 1595, 1582, 1514, 1465, 1444, 1420, 1337, 1266, 1250, 1229, 1212,
1153, 1139, 1027, 962 cm–1.
1
H NMR (CDCl3, 400 MHz): δ 7.40 (d, J = 8.1 Hz, 2H), 7.17 (d, J = 7.9 Hz, 2H), 7.077.03 (m, 2H), 7.02
(d, JAB = 16.3 Hz, 1H), 6.95 (d, JAB = 16.3 Hz, 1H), 6.86 (d, J = 8.3 Hz, 1H), 3.95 (s, 3H), 3.90 (s, 3H), 2.36
(s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 149.2, 148.9, 137.3, 134.9, 130.8, 129.5 (2C), 127.6, 126.9, 126.3 (2C),
119.8, 111.3, 108.8, 56.1, 56.0, 21.4.
119 (12).
(Z)-1,2-Dimethoxy-4-[2-(4-methylphenyl)ethenyl]benzene ((Z)-3f)
Compound (Z)-3f was isolated as a pale yellow oil.
19
Velder, J.; Ritter, S.; Lex, J.; Schmalz, H.-G. Synthesis 2006, 273 –278.
S-26
IR (neat): νmax 3003, 2919, 2835, 1601, 1580, 1514, 1463, 1419, 1258, 1236, 1173, 1134, 1027 cm–1.
1
H NMR (CDCl3, 400 MHz): δ 7.20 (d, J = 8.1 Hz, 2H), 7.07 (d, J = 7.9 Hz, 2H), 6.85 (dd, J = 8.2, 1.9 Hz,
1H), 6.81 (d, J = 1.9 Hz, 1H), 6.76 (d, J = 8.2 Hz, 1H), 6.53 (d, JAB = 12.3 Hz, 1H), 6.49 (d, JAB = 12.2 Hz,
1H), 3.87 (s, 3H), 3.64 (s, 3H), 2.36 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 148.4, 148.2, 136.8, 134.7, 130.2, 129.4, 129.0, 128.9 (2C), 128.8 (2C),
121.8, 111.8, 110.9, 55.8, 55.6, 21.3.
(10), 119 (13).
HRMS: calcd for C17H18O2Na (M+Na)+ : 277.1199, found : 277.1199.
N,N-Dimethyl-4-[2-(4-methylphenyl)ethenyl]aniline (3g)
(E)-N,N-Dimethyl-4-[2-(4-methylphenyl)ethenyl]aniline ((E)-3g) 6
Formula: C17H19N MW = 237.34 g.mol–1
Compound (E)-3g was synthesized (E)-4-(2-methoxyethenyl)-N,N-dimethylaniline (E)-1g (177.2 mg,

1.0 mmol) and p-tolylmagnesium bromide 2 (3.75 mL, 3.0 mmol, 0.80 M in THF) according to
procedure D. Purification by flash column chromatography (PE/Et2O = 90:10) afforded (E)-3g (134
mg, 0.597 mmol, 60%) as a pale green solid.
mp = 168170 °C.
IR (neat): νmax 2974, 2903, 1605, 1523, 1447, 1412, 1360, 1225, 1185, 1166, 1066, 967, 949 cm–1.
1
H NMR (CDCl3, 400 MHz): δ 7.427.37 (m, 4H), 7.14 (d, J = 7.9 Hz, 2H), 7.01 (d, JAB = 16.3 Hz, 1H),
6.90 (d, JAB = 16.3 Hz, 1H), 6.73 (d, J = 8.9 Hz, 2H), 2.98 (s, 6H), 2.35 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 150.1, 136.6, 135.5, 129.4 (2C), 127.9, 127.6 (2C), 126.2, 126.1 (2C),
124.6, 112.7 (2C), 40.7 (2C), 21.3.
111 (6).
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(Z)-N,N-Dimethyl-4-[2-(4-methylphenyl)ethenyl]aniline ((Z)-3g)6
Compound 3g was synthesized from 4-(2-methoxyethenyl)-N,N-dimethylaniline 1g (182 mg, 1.027

procedure C. Purification by flash column chromatography (PE/Et2O = 100:0 then 99:1 and then 98:2)
afforded 3g (170 mg, 0.716 mmol, 70%) as a pale yellow solid and as a mixture of (E)-3g and (Z)-3g in
a ratio E/Z = 52:48.

IR (solid state): νmax 3004, 2918, 2802, 1608, 1522, 1445, 1355, 1223, 1168, 1062, 965, 947cm–1.
Compound (Z)-3g was separated by column chromatography (PE/Et2O = 100:0 then 99:1 and then
98:2) as a pale yellow solid.
1
H NMR (CDCl3, 400 MHz): δ 7.22 (d, J = 8.3 Hz, 2H), 7.17 (d, J = 8.8 Hz, 2H), 7.04 (d, J = 7.9 Hz, 2H),
6.57 (d, J = 8.9 Hz, 2H), 6.44 (d, JAB = 12.2 Hz, 1H), 6.37 (d, JAB = 12.2 Hz, 1H), 2.92 (s, 6H), 2.31 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 149.6, 136.4, 135.4, 130.0 (2C), 129.8, 129.0 (2C), 128.8 (2C), 127.0,
125.6, 112.0 (2C), 40.5 (2C), 21.4.
111 (6).
3-Methoxy-4-(2-tolylethenyl)-N,N-diethylaniline (3h)
Compound 3h was synthesized from 1-(2-methoxy)-(2-methoxyethenyl)-N,N-diethylaniline 1h (236

mg, 1.003 mmol) and p-tolylmagnesium bromide 2 (2.174 mL, 1.50 mmol, 0.69 M in THF) according
to procedure C. Purification by flash column chromatography (PE/Et2O = 100:0 and 95:5) afforded 3h
(188.1 mg, 0.6367 mmol, 63%) as a yellow oil and as a mixture of (E)-3h and (Z)-3h in a ratio E/Z =
57:43. As the two sets of signals in the 1H and 13C NMR spectra are differentiated, an independent
description for (E)-3h and (Z)-3h is reported. Both E- and Z-isomers are differentiated by GC, MS data
for both isomers are reported.
IR (neat): νmax 2971, 2929, 1606, 1520, 1454, 1400, 1377, 1358, 1279, 1226, 1115, 1078, 1034, 968
cm–1.
HRMS: calcd for C20H26NO (M+H)+ : 296.2009, found : 296.2008.
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(E)-3-Methoxy-4-(2-tolylethenyl)-N,N-diethylaniline ((E)-3h)

1
H NMR (CDCl3, 400 MHz): δ 7.42 (d, J = 8.7 Hz, 1H), 7.38 (d, J = 8.7 Hz, 2H), 7.387.32 (m, 3H), 7.11‒
7.09 (m, 2H), 6.89 (d, J = 16.4 Hz, 1H), 6.29 (dd, J = 8.7, 2.4 Hz, 1H), 6.17 (m, 1H), 3.84 (s, 3H), 3.35 (q,
J = 7.1 Hz, 4H), 2.31 (s, 3H), 1.17 (t, J = 7.1 Hz, 6H).
13
C NMR (CDCl3, 100 MHz): δ 158.3 (2C), 148.7, 136.1, 135.5, 129.3 (2C), 128.76 (2C), 127.4, 124.3,
122.8, 104.8, 95.2, 55.6, 44.6 (2C), 21.28, 12.8 (2C).
118 (9).
(Z)-3-Methoxy-4-(2-tolylethenyl)-N,N-diethylaniline ((Z)-3h)

1
H NMR (CDCl3, 400 MHz): δ 7.24 (d, J = 8.1 Hz, 2H), 7.10 (m, 1H), 7.00 (d, J = 7.9 Hz, 2H), 6.58 (d, JAB
= 12.2 Hz, 1H), 6.38 (d, JAB = 12.2 Hz, 1H), 6.17 (m, 1H), 6.07 (dd, J = 8.6, 2.5 Hz, 1H), 3.80 (s, 3H), 3.31
(q, J = 7.1 Hz, 4H), 2.28 (s, 3H), 1.15 (t, J = 7.1 Hz, 6H).
13
C NMR (CDCl3, 100 MHz): δ 158.6 (2C), 148.6, 136.2, 135.7, 130.6, 128.78 (2C), 126.8, 126.0 (2C),
124.8, 103.9, 94.9, 55.5, 44.5 (2C), 21.33, 12.8 (2C).
118 (9).
3-[2-(4-Methylphenyl)ethenyl]pyridine (3i)20
Compound 3i was synthesized from 3-(2-methoxyethenyl)pyridine 1i (138.4 mg, 1.024 mmol) and
p-tolylmagnesium bromide 2 (1.617 mL, 1.536 mmol, 0.95 M in THF) according to procedure C.
20
Hepburn, H. B.; Melchiorre, P. Chem. Commun. 2016, 52, 35203523.
S-29
Purification by flash column chromatography (PE/EtOAc = 8:2 then 7:3) afforded 3i (101 mg, 0.517
mmol, 51%) as a pale yellow solid and as a mixture of (E)-3i and (Z)-3i in a ratio E/Z = 75:25. As the
two sets of signals in 1H and 13C NMR are not well differentiated and could not be unequivocally
attributed, NMR data are given for the mixture. Both E- and Z-isomers are differentiated by GC, MS
data for both isomers are reported.
IR (solid state): νmax 3024, 2921, 2858, 1566, 1511, 1482, 1422, 1175, 1023, 972 cm–1.
1
H NMR (CDCl3, 400 MHz): δ 8.70 (m, 0.75H), 8.498.40 (m, 1.25H), 7.79 (m, 0.75H), 7.52 (m, 0.25H),
7.41 (d, J = 8.0 Hz, 1.5H), 7.306.95 (m, 5H), 6.70 (d, JAB = 12.2 Hz, 0.25H), 6.48 (d, JAB = 12.2 Hz,
0.25H), 2.36 (s, 2.25H), 2.30 (s, 0.75H).
13
C NMR (CDCl3, 100 MHz): δ 150.3, 148.6, 148.4, 148.0, 138.3, 137.5, 135.9, 134.0, 133.6, 133.3,
133.2, 132.7, 132.6, 130.8, 129.6 (2C), 129.3, 128.7, 126.7 (2C), 125.8, 123.9, 123.6, 123.1, 21.4, 21.3.
(E)-3i: MS (EI, 70 eV): m/z (relative intensity) = 194 (M+•, 100), 180 (18), 179 (10), 152 (11), 115 (8),
96 (9), 83 (9).
(Z)-3i: MS (EI, 70 eV): m/z (relative intensity) = 194 (M+•, 100), 180 (17), 179 (11), 152 (11), 115 (9),
97 (7), 83 (8).
1-Methyl-3-[2-(4-methylphenyl)ethenyl]-1H-indole (3j)
Compound 3j was synthesized from 3-(2-methoxyethenyl)-1-methyl-1H-indole 1j (193.6 mg, 1.034

procedure C. Purification by flash column chromatography (PE/Et2O = 100:0, 98:2 and 95:5) afforded
3j (163 mg, 0.659 mmol, 64%) as a mixture of (E)-3j and (Z)-3j in a ratio E/Z = 71:29. The (E)- and (Z)-
isomers were separated by column chromatography (PE/Et2O = 99:1 and 98:2). The spectral data are
given for each isomer (E)-3j and (Z)-3j.
(E)-1-Methyl-3-[2-(4-methylphenyl)ethenyl]-1H-indole ((E)-3j)6
Compound (E)-3j was isolated as a pale yellow solid.
mp = 93–95 °C.
1071, 956 cm–1.
S-30
1
H NMR (CDCl3, 400 MHz): δ 7.98 (m, 1H), 7.42 (d, J = 8.2 Hz, 2H), 7.357.20 (m, 5H), 7.16 (d, J = 7.8
Hz, 2H), 7.07 (d, JAB = 16.4 Hz, 1H), 3.80 (s, 3H), 2.36 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 137.8, 136.3, 136.0, 129.5 (2C), 128.3, 126.4, 125.8 (2C), 125.0, 122.3,
120.7, 120.4, 120.1, 114.3, 109.7, 33.0, 21.3.
(18), 123 (13), 115 (13).
(Z)-1-Methyl-3-[2-(4-methylphenyl)ethenyl]-1H-indole ((Z)-3j)
Compound (Z)-3j was isolated as a brown gum.
1059, 1013, 958 cm–1.
1
H NMR (CDCl3, 400 MHz): δ 7.50 (m, 1H), 7.32 (d, J = 8.1 Hz, 2H), 7.287.22 (m, 2H), 7.117.07 (m,
3H), 6.99 (br s, 1H), 6.71 (dd, J = 12.1, 0.8 Hz, 1H), 6.48 (d, J = 12.1 Hz, 1H), 3.69 (s, 3H), 2.34 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 136.6, 136.5, 136.3, 129.1 (2C), 128.6 (2C), 127.9, 127.7, 126.8, 121.9,
120.9, 119.8, 119.6, 111.9, 109.3, 33.0, 21.4.
(21), 123 (14), 115 (14).
HRMS: calcd for C18H17NH (M+H)+ : 248.1434, found : 248.1434.
1-Methyl-2-[2-(4-methylphenyl)ethenyl]-1H-pyrrole (3k)
Compound 3k was synthesized from 2-(2-methoxyethenyl)-1-methyl-1H-pyrrole 1k (142.2 mg, 1.037

afforded 3k (104 mg, 0.716 mmol, 51%) as a brown oil and as a mixture of (E)-3k and (Z)-3k in a ratio
independent description for (E)-3k and (Z)-3k is reported. Both E- and Z-isomers are differentiated by
IR (neat): νmax 3016, 2918, 1628, 1509, 1481, 1425, 1303, 1088, 1057, 953 cm–1.
HRMS: calcd for C14H16N (M+H)+ : 198.1277, found : 198.1275.
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(E)-1-Methyl-2-[2-(4-methylphenyl)ethenyl]-1H-pyrrole ((E)-3k)

1
H NMR (C6D6, 400 MHz): δ 7.31 (d, J = 8.1 Hz, 2H), 7.03 (d, J = 7.9 Hz, 2H), 6.94 (d, JAB = 15.7 Hz, 1H),
6.85 (d, JAB = 16.1 Hz, 1H), 6.65 (m, 1H), 6.326.28 (m, 2H), 2.88 (s, 3H), 2.15 (s, 3H).
13
C NMR (C6D6, 100 MHz): δ 136.7, 135.9, 132.3, 129.7 (2C), 126.3 (2C), 126.0, 123.5, 117.1, 108.8,
107.5, 33.4, 21.2.
(15), 105 (30), 98 (19).
(Z)-1-Methyl-2-[2-(4-methylphenyl)ethenyl]-1H-pyrrole ((Z)-3k)

1
H NMR (C6D6, 400 MHz): δ 7.37 (d, J = 8.1 Hz, 2H), 6.92 (d, J = 7.4 Hz, 2H), 6.47 (m, 1H), 6.39 (d, JAB =
12.2 Hz, 1H), 6.30 (m, 1H), 6.216.18 (m, 2H), 2.85 (s, 3H), 2.07 (s, 3H).
13
C NMR (C6D6, 100 MHz): δ 137.0, 135.6, 129.9, 129.4 (2C), 128.9 (2C), 128.8, 122.4, 119.1, 109.9,
108.4, 33.5, 21.2.
(18), 105 (33), 98 (18).
3-[2-(4-Methylphenyl)ethenyl]furan (3l)
Formula: C13H12O MW = 184.23 g. mol–1
Compound 3l was synthesized from 3-(2-methoxyethenyl)furan 1l (142.6 mg, 1.034 mmol) and
Purification by flash column chromatography (PE 100%) afforded 3l (81.1 mg, 0.440 mmol, 43% NMR
yield) as a mixture of (E)-3l and (Z)-3l in a ratio E/Z = 89:11, contaminated with 4,4’-dimethyl-1,1’-
S-32
biphenyl. Spectral data are only given for the major stereoisomer (E)-3l which was isolated as a pure
compound as a light brown solid.
(E)-3-[2-(4-Methylphenyl)ethenyl]furan ((E)-3l)21
mp = 119–121 °C.
IR (solid state): νmax 3140, 3013, 2916, 1506, 1153, 1072, 1019, 967 cm–1.
1
H NMR (CDCl3, 400 MHz): δ 7.52 (d, J = 0.5 Hz, 1H), 7.41 (m, 1H), 7.35 (d, J = 8.1 Hz, 2H), 7.15 (d, J =
8.0 Hz, 2H), 6.93 (d, JAB = 16.2 Hz, 1H), 6.80 (d, JAB = 16.2 Hz, 1H), 6.66 (m, 1H), 2.35 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 143.8, 140.8, 137.3, 134.7, 129.5 (2C), 128.5, 126.2 (2C), 124.8, 117.6,
107.5, 21.4.
(24), 77 (30).
3-[2-(4-Methylphenyl)ethenyl]thiophene (3m)
Formula: C13H12S MW = 200.30 g.mol–1
Compound 3m was synthesized from 3-(2-methoxyethenyl)furan 1m (161.1 mg, 1.034 mmol) and
Purification by flash column chromatography (PE 100%) afforded 3m (101 mg, 0.504 mmol, 49% NMR
yield) as a mixture of (E)-3m and (Z)-3m in a ratio E/Z = 76:24, contaminated with 4,4’-dimethyl-1,1’-
biphenyl. Spectral data are only given for the major stereoisomer (E)-3m which was isolated as a
pure compound as a pale yellow solid.
(E)-3-[2-(4-Methylphenyl)ethenyl]thiophene ((E)-3m)22
mp = 149–150 °C.
IR (solid state): νmax 3094, 3024, 2913, 2856, 1506, 967 cm–1.
1
H NMR (CDCl3, 400 MHz): δ 7.38 (d, J = 8.3 Hz, 2H), 7.357.30 (m, 2H), 7.24 (m, 1H), 7.16 (d, J = 7.8
Hz, 2H), 7.09 (d, JAB = 16.3 Hz, 1H), 6.93 (d, JAB = 16.3 Hz, 1H), 2.36 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 140.4, 137.5, 134.7, 129.5 (2C), 128.8, 126.3 (2C), 126.2, 125.1, 122.10,
122.06, 21.4.
21
Chen, Y.-Z.; Ni, C.-W.; Teng, F.-L.; Ding, Y.-S.; Lee, T.-H.; Ho, J.-H. Tetrahedron 2014, 70, 17481762.
22
Kantam, M. L.; Reddy, P. V.; Srinivas, P.; Bhargava, S. Tetrahedron Lett. 2011, 52, 4490.
S-33
(16), 99 (20).
1-Methyl-4-(undec-1-en-1-yl)benzene (3n)
Compound 3n was synthesized from 1-methoxyundec-1-ene 1n (92.6 mg, 0.502 mmol) and
Purification by flash column chromatography (PE 100%) afforded 3n (72 mg, 0.295 mmol, 59%) as a
clear oil and as a mixture of (E)-3n and (Z)-3n in a ratio E/Z = 53:47. As the two sets of signals in the
1
H NMR spectrum are differentiated, an independent description for (E)-3n and (Z)-3n is reported.
Both E- and Z-isomers are differentiated by GC, MS data for both isomers are reported.
IR (neat): νmax 2955, 2923, 2853, 1512, 1465, 964 cm–1.

13
C NMR (CDCl3, 100 MHz): δ 136.5, 136.2, 135.3, 135.1, 132.7, 130.4, 129.6, 129.3 (2C), 128.9 (2C),
128.8 (2C), 128.6, 125.9 (2C), 33.2, 32.1, 30.2, 29.75, 29.73, 29.70, 29.68, 29.60, 29.53, 29.50, 29.47,
29.40, 28.8, 22.8 (2C), 21.29, 21.25, 14.3 (2C).
HRMS: calcd for C18H29 (M+H)+ : 245.2264, found : 245.2254.
(E)-1-Methyl-4-(undec-1-en-1-yl)benzene ((E)-3n)
1
6.18 (dt, J = 15.5, 6.8 Hz, 1H), 2.34 (s, 3H), 2.20 (qapp, J = 7.0 Hz, 2H), 1.531.42 (m, 2H), 1.401.22 (m,
12H), 0.90 (t, J = 6.5 Hz, 3H).
(13), 116 (11), 115 (12), 105 (23), 91 (21).
(Z)-1-Methyl-4-(undec-1-en-1-yl)benzene ((Z)-3n)
1
5.63 (dt, J = 11.7, 7.2 Hz, 1H), 2.36 (s, 3H), 2.362.31 (m, 2H), 1.531.41 (m, 2H), 1.401.22 (m, 12H),
0.90 (t, J = 6.5 Hz, 3H).
(14), 116 (11), 115 (13), 105 (24), 91 (22).
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1,3,5-Trimethyl-2-(2-phenylethenyl)benzene (6a)
Compound 6a was synthesized from (2-methoxyethenyl)benzene 1a (103.1 mg, 0.768 mmol) and
(2,4,6-trimethylphenyl)magnesium bromide 5a (2.62 mL, 1.153 mmol, 0.44 M in THF) according to
procedure C. Purification by flash column chromatography (PE 100%) afforded 6a (139 mg, 0.625
mmol, 81%) as a pale yellow oil and as a mixture of (E)-6a and (Z)-6a in a ratio E/Z = 63:37. The (E)-
and (Z)-isomers were separated by preparative TLC (pent 100%). The spectral data are given for each
stereoisomer (E)-6a and (Z)-6a. The NMR spectra of (Z)-6a are contaminated with 2,2',4,4',6,6'-
hexamethyl-1,1'-biphenyl.
(E)-1,3,5-Trimethyl-2-(2-phenylethenyl)benzene ((E)-6a)23
The stereoisomer (E)-6a was isolated as a beige solid.
mp = 5153 °C.
IR (neat): νmax 3025, 2947, 2917, 2859, 1639, 1613, 1450, 1378, 1075, 1017, 971 cm–1.
1
H NMR (CDCl3, 400 MHz): δ 7.48 (d, J = 7.4 Hz, 2H), 7.34 (tapp, J = 7.6 Hz, 2H), 7.24 (tapp, J = 7.3 Hz,
1H), 7.09 (d, J = 16.6 Hz, 1H), 6.89 (s, 2H), 6.57 (d, J = 16.6 Hz, 1H), 2.33 (s, 6H), 2.28 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 137.9, 136.4, 136.3 (2C), 134.1, 133.8, 128.9 (2C), 128.8 (2C), 127.6,
127.1, 126.4 (2C), 21.14 (2C), 21.11.
(75), 191 (18), 129 (26), 128 (14), 115 (27), 96 (13), 91 (14), 89 (15).
(Z)-1,3,5-Trimethyl-2-(2-phenylethenyl)benzene ((Z)-6a)24
IR (neat): νmax 3031,2957, 2920, 2856, 1695, 1494, 1479, 1448, 1376, 1324, 1166, 1030, 915 cm–1.
1
H NMR (CDCl3, 400 MHz): δ 7.147.09 (m, 3H), 7.016.99 (m, 2H), 6.85 (s, 2H), 6.61 (d, J = 12.2 Hz,
1H), 6.50 (d, J = 12.2 Hz, 1H), 2.29 (s, 3H), 2.11 (s, 6H).
13
C NMR (CDCl3, 100 MHz): δ 137.8, 136.5, 135.6 (2C), 134.2, 131.1, 129.0, 128.4 (2C), 128.3 (2C),
128.2 (2C), 127.2, 21.2, 20.3 (2C).
23
Barder, T. E.; Walker, S. D.; Martinelli, J. R.; Buchwald, S. L. J. Am. Chem. Soc. 2005, 127, 46854696.
24
Ilies, L.; Yoshida, T.; Nakamura, E. J. Am. Chem. Soc., 2012, 134, 1695116954.
S-35
(74), 191 (18), 129 (24), 128 (13), 115 (24), 96 (10), 91 (13), 89 (13).
1-Methoxy-4-(2-phenylethenyl)benzene (6b)
Compound 6b was synthesized from (2-methoxyethenyl)benzene 1a (137.7 mg, 1.026 mmol) and
4-methoxyphenylmagnesium bromide 5b (4.161 mL, 1.539 mmol, 0.37 M in THF) according to
afforded 6b (183.6 mg, 0.873 mmol, 85% NMR yield) as a mixture of (E)-6b and (Z)-6b in a ratio E/Z =
59:41, contaminated with 4,4’-dimethoxy-1,1’-biphenyl (19% w/w). The (E)- and (Z)-isomers were
separated by preparative TLC (PE/Et2O = 95:5). The spectral data are given for each stereoisomer (E)-
6b and (Z)-6b.
(E)-1-Methoxy-4-(2-phenylethenyl)benzene ((E)-6b)25
Compound (E)-6b was isolated as a white solid.
mp = 131–133 °C.
967 cm–1.
1
H NMR (CDCl3, 400 MHz): δ 7.507.43 (m, 4H), 7.367.32 (m, 2H), 7.23 (m, 1H), 7.06 (d, JAB = 16.3
Hz, 1H), 6.97 (d, JAB = 16.3 Hz, 1H), 6.916.88 (m, 2H), 3.82 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 159.5, 137.8, 130.3, 128.8 (2C), 128.4, 127.9 (2C), 127.3, 126.8, 126.4
(2C), 114.3 (2C), 55.5.
(29), 152 (21), 89 (11).
(Z)-1-Methoxy-4-(2-phenylethenyl)benzene ((Z)-6b)26
25
Zhong, J.-J.; Liu, Q.; Wu, C.-J.; Meng, Q.-Y.; Gao, X.-W.; Li, Z.-J.; Chen, B.; Tung, C.-H.; Wu, L.-Z. Chem.
Commun. 2016, 52, 1800–1803.
26
Das, M.; O’Shea, D. F. Org. Lett. 2016, 16, 336–339.
S-36
Compound (Z)-6b was isolated as a clear oil.
IR (neat): νmax 3006, 2954, 2930, 2835, 1606, 1510, 1492, 1461, 1445, 1300, 1250, 1176, 1109, 1034
cm–1.
1
H NMR (CDCl3, 400 MHz): δ 7.287.16 (m, 7H), 6.776.73 (m, 2H), 6.53 (d, JAB = 12.3 Hz, 1H), 6.50 (d,
JAB = 12.3 Hz, 1H), 3.78 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 158.8, 137.8, 130.3 (2C), 129.9, 129.8, 129.0 (2C), 128.9, 128.4 (2C),
127.0, 113.7 (2C), 55.3.
(31), 152 (24), 89 (11).
1,2-(2,3-Dihydro-1,4-dioxane)-4-(2-phenylethenyl)benzene (6c)
Compound 6c was synthesized from (2-methoxyethenyl)benzene 1a (134.2 mg, 1.0 mmol) and 2,3-
dihydro-1,4-benzodioxine magnesium bromide 5c (4.545 mL, 1.5 mmol, 0.33 M in THF) according to
procedure C. Purification by flash column chromatography (Pent/Et2O = 100:0 then 98:2) afforded 6c
(148.3 mg, 0.6225 mmol, 62%) as a clear oil and as a mixture of (E)-6c and (Z)-6c in a ratio E/Z =
72:28, contaminated with 2,3-dihydrobenzo-1,4-dioxine (15% w/w). As the two sets of signals in the
1
H and 13C NMR spectra are differentiated, an independent description for (E)-6c and (Z)-6c is
reported. Both E- and Z-isomers are differentiated by GC, MS data for both isomers are reported.
IR (neat): νmax 3025, 2929, 2873, 1581, 1506, 1457, 1448, 1429, 1289, 1248, 1204, 1155, 1067, 1050,
960, 921 cm–1.
HRMS: calcd for C16H15O2 (M+H)+ : 239.1067, found : 239.1065.
(E)-1,2-(2,3-Dihydro-1,4-dioxane)-4-(2-phenylethenyl)benzene ((E)-6c)

1
H NMR (CDCl3, 400 MHz): δ 7.46‒7.44 (m, 2H), 7.33‒7.16 (m, 3H), 7.03 (d, J = 2.1 Hz, 1H), 6.99 (dd, J
= 8.4, 2.1 Hz, 1H), 6.98 (d, JAB = 16.3 Hz, 1H), 6.92 (d, JAB = 16.4 Hz, 1H), 6.83 (d, J = 8.4 Hz, 1H), 4.21 (s,
4H).
13
C NMR (CDCl3, 100 MHz): δ 143.7, 143.5, 137.6, 131.2, 128.7 (2C), 128.2, 127.4, 127.2, 126.4 (2C),
120.1, 117.5, 115.1, 64.5, 64.4.
51 (9).
S-37
(Z)-1,2-(2,3-Dihydro-1,4-dioxane)-4-(2-phenylethenyl)benzene ((Z)-6c)

1
H NMR (CDCl3, 400 MHz): δ 7.33‒7.16 (m, 5H), 6.77 (d, J = 2.0 Hz, 1H), 6.73 (dd, J = 8.4, 2.0 Hz, 1H),
6.68 (d, J = 8.3 Hz, 1H), 6.49 (d, JAB = 12.3 Hz, 1H), 6.44 (d, JAB = 12.2 Hz, 1H), 4.19‒4.14 (m, 4H).
13
C NMR (CDCl3, 100 MHz): δ 143.2, 142.9, 137.5, 130.7, 129.7, 129.3, 128.9 (2C), 128.3 (2C), 127.1,
122.4, 117.7, 117.0, 64.46, 64.3.
51 (9).
N,N-Dimethyl-3-(2-phenylethenyl)aniline (6d)
Compound 6d was synthesized from (2-methoxyethenyl)benzene 1a (134.2 mg, 1.0 mmol) and
3-dimethylaniline magnesium bromide 5d (8.44 mL, 2.616 mmol, 0.31 M in THF) according to
procedure C. For the synthesis of this compound, Ni(OAc)2 (8.839 mg, 0.05 mmol) and
triphenylphosphine oxide (56.79 mg, 0.2 mmol) were needed. Purification by flash column
chromatography (PE/Et2O = 100:0 then 95:5) afforded 6d (0.53 mmol, 53%) as a yellow oil and as a
mixture of (E)-6d and (Z)-6d in a ratio E/Z = 70:30, contaminated with dimethylaniline (12% w/w).
The (E)- and (Z)-isomers were separated by preparative TLC plate (PE/Et2O = 95:5). The spectral data
are given for each stereoisomer (E)-6d and (Z)-6d.
(E)-N,N-Dimethyl-3-(2-phenylethenyl)aniline ((E)-6d)
Compound (E)-6d was isolated as a yellow oil.
IR (neat): νmax 3055, 3025, 2919, 1596, 1575, 1498, 1447, 1354, 1232, 1176, 1156, 996, 961 cm–1.
1
H NMR (CDCl3, 400 MHz): δ 7.52 (d, J = 7.5 Hz, 2H), 7.52 (tapp, J = 7.6 Hz, 2H), 7.25‒7.22 (m, 2H), 7.10
(s, 2H), 6.93 (d, J = 7.6 Hz, 1H), 6.86 (s, 1H), 6.93 (dd, J = 8.2, 2.3 Hz, 1H), 3.00 (s, 6H).
13
C NMR (CDCl3, 100 MHz): δ 151.1, 138.2, 137.7, 129.8, 129.5, 128.8 (2C), 128.4, 127.6, 126.6 (2C),
115.2, 112.4, 111.0, 40.9 (2C).
89 (8).
S-38
(Z)-N,N-Dimethyl-3-(2-phenylethenyl)aniline ((Z)-6d)
Compound (Z)-6d was isolated as a yellow oil.
IR (neat): νmax 3055, 3008, 2920, 2850, 2801, 1597, 1573, 1493, 1444, 1434, 1349, 1230, 1177, 1130,
1061, 997 cm–1.
1
H NMR (CDCl3, 400 MHz): δ 7.30‒7.27 (m, 2H), 7.24‒7.19 (m, 2H), 7.16 (m, 1H), 7.10 (tapp, J = 7.9 Hz,
1H), 6.64‒6.63 (m, 2H), 6.60 (m, 1H), 6.57 (s, 2H), 2.79 (s, 6H).
13
C NMR (CDCl3, 100 MHz): δ 150.6, 137.9, 137.8, 131.3, 129.9, 129.1 (2C), 129.0, 128.3 (2C), 127.0,
117.8, 113.3, 111.9, 40.6 (2C).
89 (8).
N,N-Dimethyl-2-(2-phenylethenyl)aniline (6e)
Compound 6e was synthesized from (2-methoxyethenyl)benzene 1a (134.2 mg, 1.0 mmol) and
2-dimethylaniline magnesium bromide 5e (6.90 mL, 2.0 mmol, 0.29 M in THF) according to procedure
C. For the synthesis of this compound, Ni(OAc)2 (8.8 mg, 0.0498 mmol) and triphenylphosphine oxide
(8.8 mg, 0.0498 mmol) were needed. Purification by flash column chromatography (PE/Et2O = 100:0
then 99:1) afforded 6e (157.7 mg, 0.706 mmol, 71%) as a pale yellow oil and as a mixture of (E)-6e
and (Z)-6e in a ratio E/Z = 70:30, contaminated with dimethylaniline (25% w/w). As the two sets of
signals in the 1H and 13C NMR spectra are differentiated, an independent description for (E)-6e and
(Z)-6e is reported. Both E- and Z-isomers are differentiated by GC, MS data for both isomers are
reported.
IR (neat): νmax 3024, 2939, 2860, 2828, 2780, 1594, 1484, 1451, 1431, 1317, 1188, 1155, 1144, 1096,
1049, 974, 947 cm–1.
S-39
(E)-N,N-Dimethyl-2-(2-phenylethenyl)aniline ((E)-6e)

1
H NMR (CDCl3, 400 MHz): δ 7.59‒7.55 (m, 3H), 7.47 (d, J = 16.5 Hz, 1H), 7.37‒7.33 (m, 2H), 7.26‒
7.13 (m, 2H), 7.05‒7.00 (m, 2H), 7.03 (d, J = 16.2 Hz, 1H), 2.75 (s, 6H).
13
C NMR (CDCl3, 100 MHz): δ 152.2, 138.3, 131.5, 130.6, 128.8 (2C), 128.33, 128.14, 126.95, 126.9,
126.6 (2C), 122.5, 118.2, 44.8 (2C).
77 (10).
(Z)-N,N-Dimethyl-2-(2-phenylethenyl)aniline ((Z)-6e)

1
H NMR (CDCl3, 400 MHz): δ 7.32‒7.28 (m, 2H), 7.26‒7.13 (m, 5H), 6.99 (m, 1H), 6.76 (tdapp, J = 7.6,
1.0 Hz, 1H), 6.66 (d, J = 12.2 Hz, 1H), 6.55 (d, J = 12.2 Hz, 1H), 2.82 (s, 6H).
13
C NMR (CDCl3, 100 MHz): δ 152.2, 137.4, 130.7, 129.8, 128.9 (2C), 128.26 (2C), 128.08, 127.4 (2C),
127.00, 121.3, 117.4, 44.3 (2C).
77 (12).
(4-Methylpenta-1,3-dien-1-yl)benzene (6f)
Compound 6f was synthesized from (2-methoxyethenyl)benzene 1a (100.7 mg, 0.751 mmol) and
(2-methylprop-1-en-1-yl)magnesium bromide 5f (2.963 mL, 1.126 mmol, 0.38 M in THF) according to
procedure C. Purification by flash column chromatography (PE 100%) afforded 6f (85 mg, 0.537
mmol, 72%) as a clear oil and as a mixture of (E)-6f and (Z)-6f in a ratio E/Z = 75:25. As the two sets of
signals in the 1H and 13C NMR spectra are differentiated, an independent description for (E)-6f and
(Z)-6f is reported. Both E- and Z-isomers are differentiated by GC, MS data for both isomers are
reported.
IR (neat): νmax 3029, 2966, 2910, 2854, 1644, 1596, 1491, 1448, 1377, 1354, 1181, 1072, 1043, 1028,
984, 953 cm–1.
S-40
(E)-(4-Methylpenta-1,3-dien-1-yl)benzene ((E)-6f)27

1
H NMR (CDCl3, 400 MHz): δ 7.417.24 (m, 4H), 7.19 (m, 1H), 6.98 (dd, J = 15.5, 11.0 Hz, 1H), 6.41 (d,
J = 15.5 Hz, 1H), 5.99 (br d, J = 12.9 Hz, 1H), 1.85 (s, 3H), 1.83 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 138.2, 136.6, 129.7, 128.7 (2C), 127.0, 126.2 (2C), 125.8, 125.6, 26.4,
18.7.
(61), 127 (11), 115 (29), 91 (14), 77 (10).
(Z)-(4-Methylpenta-1,3-dien-1-yl)benzene ((Z)-6f)27

1
H NMR (CDCl3, 400 MHz): δ 7.417.24 (m, 4H), 7.19 (m, 1H), 6.466.33 (m, 2H), 6.31 (d, J = 11.2 Hz,
1H), 1.82 (s, 3H), 1.81 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 138.5, 138.1, 129.2 (2C), 128.3 (2C), 127.2, 126.6 (2C), 121.6, 26.5, 18.5.
(68), 127 (12), 115 (31), 91 (14), 77 (11).
(3-Phenylprop-1-en-1-yl)benzene (6g)28
Compound 6g was synthesized from (2-methoxyethenyl)benzene 1a (135.6 mg, 1.011 mmol) and
benzylmagnesium chloride 5g (0.948 mL, 1.516 mmol, 1.60 M in THF) according to procedure C.
Purification by flash column chromatography (PE 100%) afforded 6g (135 mg, 0.695 mmol, 69%) as a
clear oil and as a mixture of (E)-6g and (Z)-6g in a ratio E/Z = 82:18. Both E- and Z-isomers are
differentiated by GC, MS data for both isomers are reported and the IR data are reported for both
isomers. The NMR data are only given for the major stereoisomer (E)-6g contaminated with 1,2-
diphenylethane.
27
Tamura, R.; Saegusa, K.; Kakihana, M.; Oda, D. J. Org. Chem. 1988, 53, 27232728.
28
Yang, Z.; Kumar, R. K.; Liao, P.; Liu, Z.; Li, X.; Bi, X. Chem. Commun. 2016, 52, 59365939.
S-41
IR (neat): νmax 3082, 3060, 3025, 2898, 1600, 1494, 1452, 1430, 1155, 1074, 1029, 964 cm–1.
For (E)-6g:
1
H NMR (CDCl3, 400 MHz): δ 7.377.16 (m, 10H), 6.45 (d, J = 15.8 Hz, 1H), 6.35 (dt, J = 15.7, 6.6 Hz,
1H), 3.54 (d, J = 6.6 Hz, 2H).
13
C NMR (CDCl3, 100 MHz): δ 140.3, 137.6, 131.2, 129.4, 128.8 (2C), 128.6 (4C), 127.2, 126.32, 126.27
(2C), 39.5.
(21), 116 (47), 115 (82), 103 (20), 91 (34), 89 (14), 77 (14), 65 (16).
For (Z)-6g:
(21), 116 (54), 115 (91), 103 (21), 91 (38), 89 (16), 77 (17), 65 (20).
(2-Cyclopropylethenyl)benzene (6h)
Compound 6h was synthesized from (2-methoxyethenyl)benzene 1a (134.2 mg, 1.0 mmol) and
cyclopropylmagnesium bromide 5h (2.586 mL, 1.5 mmol, 0.58 M in THF) according to procedure C.
Purification by flash column chromatography (pent 100%) afforded 6h (88.9 mg, 0.62 mmol, 62%) as
a clear oil and as a mixture of (E)-6h and (Z)-6h in a ratio E/Z = 62:38. As the two sets of signals in the
1
H and 13C NMR spectra are differentiated, an independent description for (E)-6h and (Z)-6h is
reported. Both E- and Z-isomers are differentiated by GC, MS data for both isomers are reported.
IR (neat): νmax 3081, 3005, 1650, 1600, 1491, 1448, 1072, 1047, 1019, 954, 937 cm–1.
(E)- (2-Cyclopropylethenyl)benzene ((E)-6h)29

1
H NMR (CDCl3, 400 MHz): δ 7.44‒7.41 (m, 2H), 7.35‒7.13 (m, 3H), 6.46 (d, J = 15.8 Hz, 1H), 5.72 (dd,
J = 15.8, 8.9 Hz, 1H), 1.56 (m, 1H), 0.84‒0.78 (m, 2H), 0.52‒0.44 (m, 2H).
13
C NMR (CDCl3, 100 MHz): δ 137.9, 135.0, 128.6 (2C), 127.53, 126.7, 125.7 (2C), 14.7, 7.4 (2C).
51 (10).
29
Gandon, V.; Bertus, P.; Szymoniak, J. Eur. J. Org. Chem. 2000, 3713‒3719.
S-42
(Z)-(2-Cyclopropylethenyl)benzene ((Z)-6h)30

1
H NMR (CDCl3, 400 MHz): δ 7.35‒7.13 (m, 5H), 6.34 (d, J = 11.5 Hz, 1H), 5.06 (dd, J = 11.5, 9.9 Hz,
1H), 1.88 (m, 1H), 0.84‒0.78 (m, 2H), 0.52‒0.44 (m, 2H).
13
C NMR (CDCl3, 100 MHz): δ 138.1, 136.9, 128.8 (2C), 128.3 (2C), 127.50, 126.5, 11.2, 8.2 (2C).
MS (EI, 70 eV): m/z (relative intensity) = 144 (M+•, 45), 129 (100), 115 (34), 91 (13), 71 (9), 66 (11), 51
(11).
N-Methyl-3-(2-phenylethenyl)-7-azaindole (6i)
Formula: C16H14N2 MW = 234.30 g.mol–1
Compound 6i was synthesized from (2-methoxyethenyl)benzene 1a (134.2 mg, 1.0 mmol) and 3-(N-
methyl-7-azaindole)magnesium bromide 5i (8.0 mL, 2.4 mmol, 0.3 M in THF) according to procedure
C. For the synthesis of this compound, Ni(OAc)2 (8.84 mg, 0.0475 mmol) and triphenylphosphine
oxide (56.79 mg, 0.2 mmol) were needed to afford 6i as a mixture of (E)-6i and (Z)-6i in a ratio E/Z =
99:1 obtained by analyzing the 1H NMR spectrum of the crude. Purification by flash column
chromatography (PE/Et2O = 98:2 then 70:30) afforded (E)-6i (108 mg, 0.461 mmol, 46%) as a yellow
solid.
mp = 111113 °C.
IR (neat): νmax 3032, 2919, 1636, 1593, 1567, 1530, 1495, 1486, 1458, 1442, 1407, 1350, 1296, 1185,
1150, 1072, 1028, 952, 908 cm–1.
1
H NMR (CDCl3, 400 MHz): δ 8.37 (dd, J = 4.7, 1.5 Hz, 1H), 8.24 (dd, J = 7.9, 1.5 Hz, 1H), 7.49 (dapp, , J =
7.3 Hz, 2H), 7.36‒7.30 (m, 3H), 7.24‒7.19 (m, 2H), 7.14 (dd, J = 7.9, 4.7 Hz, 1H), 7.05 (d, J = 16.4 Hz,
1H), 3.87 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 148.7, 143.6, 138.3, 128.8 (2C), 128.6, 128.5, 126.9, 125.9 (2C), 125.7,
121.4, 118.5, 116.2, 112.6, 31.4.
117 (10), 116 (10), 109 (12).
HRMS: calcd for C16H15N2 (M+H)+ : 235.1230, found : 235.1231.
30
Nishibayashi, R.; Kurahashi, T.; Matsubara, S. Synlett, 2014, 1287‒1290.
S-43
2-(3-Methylbut-1-en-1-yl)naphthalene (6j)31
Formula: C15H16 Mw = 196.29 g.mol–1
Compound 6j was synthesized from 2-(2-methoxyethenyl)naphthalene 1o (185.2 mg, 1.005 mmol)

(134.2 mg, 1.0 mmol) and isopropylmagnesium chloride 5j (1.257 mL, 1.508 mmol, 1.20 M in THF)
according to procedure C. Purification by flash column chromatography (PE 100%) afforded 6j (35
mg, 0.178 mmol, 18% as a yellow viscous solid and as a mixture of (E)-6j and (Z)-6j in a ratio E/Z >
95:5. As most of NMR signals corresponding to (Z)-6j were too weak to be seen or unequivocally
attributed, they are not shown in the description. Both E- and Z-isomers are differentiated by GC, MS
data for both isomers are reported.
IR (neat): νmax 3056, 2985, 2926, 2867, 1598, 1508, 1463, 1361, 966, 891, 860, 809, 743 cm –1.
For (E)-6j:
1
H NMR (CDCl3, 400 MHz): δ 7.797.75 (m, 3H), 7.68 (d, J = 1.2 Hz, 1H), 7.58 (dd, J = 8.6, 1.7 Hz, 1H),
7.467.38 (m, 2H), 6.50 (dd, J = 15.9, 0.6 Hz, 1H), 6.33 (dd, J = 15.9, 6.8 Hz, 1H), 2.52 (m, 1H), 1.13 (d,
J = 6.8 Hz, 6H).
13
C NMR (CDCl3, 100 MHz): δ 138.7, 135.6, 133.9, 132.8, 128.2, 127.9, 127.8, 127.1, 126.2, 125.5 (2C),
123.8, 31.8, 22.6 (2C).
165 (42), 153 (14), 152 (11), 141 (14), 128 (14), 89 (11).
For (Z)-6j:
165 (45), 153 (15), 152 (11), 141 (16), 128 (15), 89 (14).
31
Dong, D.-J.; Li, Y.; Wang, J.-Q.; Tian, S.-K. Chem. Commun. 2011, 47, 21582160.
S-44
(E)-N,N-Dimethyl-4-(2-phenylethenyl)benzene ((E)-6k)32
Compound (E)-6k was synthesized from (E)-(2-methoxyethenyl)benzene (113.2 mg, 0.844 mmol) and
4-N,N-dimethylphenylmagnesium bromide 5k (11 mL, 2.53 mmol, 0.23 M in THF) according to
procedure D. Purification by column chromatography (PE 100%) afforded (E)-6k (93.18 mg, 0.417
mmol, 49%) as a white solid contaminated with dimethylaniline (67% w/w). Compound (E)-6k was
partially isolated by column chromatography (PE 100%) as a pure compound as a white solid.
mp = 146148 °C.
IR (neat): νmax 2884, 2801, 1606, 1592, 1522, 1446, 1354, 1223, 1190, 1166, 1063, 963, 908 cm–1.
1
H NMR (CDCl3, 400 MHz): δ 7.49 (d, J = 7.2 Hz, 2H), 7.43 (d, J = 8.6 Hz, 2H), 7.34 (tapp, J = 7.7 Hz, 2H),
7.21 (m, 1H), 7.06 (d, JAB = 16.3 Hz, 1H), 6.93 (d, JAB = 16.3 Hz, 1H), 6.73 (d, J = 8.8 Hz, 2H), 2.99 (s, 6H).
13
C NMR (CDCl3, 100 MHz): δ 150.2, 138.3 (2C), 128.9, 128.7 (2C), 127.7 (2C), 126.8, 126.2 (2C),
124.6, 112.6 (2C), 40.7 (2C).
89 (10).
(E)-1,2,3-Trimethoxy-5-(4-methoxystyryl)benzene (DMU-212)33
Compound DMU-212 was synthesized from (E)-1,2,3-trimethoxy-5-(2-methoxyethenyl)benzene 1p

(135 mg, 0.602 mmol) and 4-methoxyphenylmagnesium bromide 5b (5.16 mL, 1.806 mmol, 0.35 M in
THF) according to procedure D. Purification by flash column chromatography (PE/Et2O = 95:5)
afforded DMU-212 (121.5 mg, 0.4045 mmol, 67%) as a beige solid.
mp = 154156 °C.
IR (neat) : νmax 2935, 2835, 1605, 1580, 1509, 1453, 1416, 1343, 1320, 1300, 1243, 1233, 1175, 1123,
1031, 1005 cm–1.
32
Tanaka, S.; Mori, A. Eur. J. Org. Chem. 2014, 11671171.
33
Das, M.; Manvar, A.; Jacolot, M.; Blangetti, M.; Jones, R.C.; O'Shea, D. F. Chem.Eur. J. 2015, 21, 87378740.
S-45
1
H NMR (CDCl3, 400 MHz): δ 7.467.43 (m, 2H), 6.97 (d, J = 16.2 Hz, 1H), 6.926.88 (m, 2H), 6.90 (d, J
= 16.2 Hz, 1H), 6.72 (s, 2H), 3.91 (s, 6H), 3.87 (s, 3H), 3.83 (s, 3H).
13
C NMR (CDCl3, 100 MHz): δ 159.4, 153.5 (2C), 137.7, 133.6, 130.1, 127.9, 127.7 (2C), 126.7, 114.3
(2C), 103.4 (2C), 61.1, 56.2 (2C), 55.4.
(17), 128 (14), 121 (9), 106 (7), 85 (8).
3. Stereoselectivity studies of the cross-coupling reaction

The alkenyl methyl ether (Z)-1a was treated with p-tolylmagnesium bromide 2 under the optimized
catalytic conditions, the conversion (Z)-1a, the yield and E/Z ratio of 3a and the yield of 4 overtime
are reported in Table 1.
Yielda (%) Yielda (%)

entry time (h) τca (%)
3a (E/Z)a 4
1 0.33 100 76 (12:88) 18
2 1 100 77 (11:89) 20
3 3 100 81 (13:87) 19
4 12 100 78 (18:82) 19
5 24 100 80 (23:77) 19
6 72 100 80 (29:71) 17
a
Conversion, yield and E/Z ration were determined by 1H NMR using CH2Br2 as an internal standard.
Table 1
S-46
ALKENYL METHYL ETHERS
1H NMR, 400 MHz, CDCl3
13C NMR, 100 MHz, CDCl3
S-47
S-48
S-49
S-50
S-51
S-52
S-53
S-54
1H NMR, 400 MHz, C6D6
13C NMR, 100 MHz, C6D6
S-55
S-56
S-57
S-58
S-59
1H NMR, 400 MHz, C6D6, contaminated with (O)PPh3 (*)
13C NMR, 100 MHz, C6D6, contaminated with (O)PPh3 (*)
S-60
S-61
S-62
S-63
S-64
STILBENE PRODUCTS
1H NMR, 400 MHz, CDCl3 : contaminated with 1,4-diphenylbuta-1,3-diene (*)
13C NMR, 100 MHz, CDCl3 : contaminated with 1,4-diphenylbuta-1,3-diene (*)
S-65
1H NMR, 400 MHz, CDCl3 : contaminated with 4,4'-dimethyl-1,1'-biphenyl (*)
13C NMR, 100 MHz, CDCl3 : contaminated with 4,4'-dimethyl-1,1'-biphenyl (*)
S-66
S-67
S-68
S-69
S-70
S-71
S-72
S-73
S-74
1H NMR, 400 MHz, CDCl3 (contains some impurities)
13C NMR, 100 MHz, CDCl3 (contains some impurities)
S-75
S-76
S-77
S-78
S-79
S-80
S-81
S-82
S-83
S-84
13C NMR, 100 MHz, CDCl3 (contains some impurities (*))
S-85
S-86
1H NMR, 400 MHz, CDCl3 : contaminated with 2,2',4,4',6,6'-hexamethyl-1,1'-biphenyl (*)
13C NMR, 100 MHz, CDCl3 : contaminated with 2,2',4,4',6,6'-hexamethyl-1,1'-biphenyl (*)
S-87
1H NMR, 400 MHz, CDCl3 (contains some impurities (*))
S-88
S-89
S-90
S-91
S-92
S-93
S-94
1H NMR, 400 MHz, CDCl3 contaminated by 1,2-diphenylethane (*)
13C NMR, 100 MHz, CDCl3 contaminated by 1,2-diphenylethane
S-95
S-96
S-97
S-98
S-99
S-100

Ol8b00313 Si 001

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Nickel-Catalyzed System for the Cross-

Coupling of Alkenyl Methyl Ethers with

1. Synthesis of alkenyl methyl ethers by Wittig reaction……………………..S-3

2. Nickel-catalyzed Kumada coupling of alkenyl methyl ethers……….....S-19

3. Stereoselectivity studies of the cross-coupling reaction………………….S-46

4. Copies of the 1H and 13C NMR spectra…………………………………………….S-47

To a suspension of (methoxymethyl)triphenylphosphonium chloride (1.2 equiv) in THF (c = 0.25 M) at

Formula: C9H10O MW= 134.18 g.mol–1

Compound (E)-1a was isolated as a clear oil.

Formula: C9H10O MW = 134.18 g.mol–1

Compound (Z)-1a was isolated as a clear oil.

Compound 1b was synthesized from 4-benzyloxybenzaldehyde (1.09 g, 5.00 mmol) according to

For both (E)- and (Z)-isomers:

Formula: C16H16O2 MW = 240.30 g.mol–1

Formula: C16H16O2 MW = 240.30 g.mol–1

For both (E)- and (Z)-isomers:

Formula: C10H12O2 MW = 164.20 g.mol–1

Formula: C10H12O2 MW = 164.20 g.mol–1

For both (E)- and (Z)-isomers:

HRMS: calcd for C10H13O2 (M+H)+ : 165.0910 , found : 165.0909.

Formula: C10H12O2 MW = 164.20 g.mol–1

Formula: C10H12O2 MW = 164.20 g.mol–1

For both (E)- and (Z)-isomers:

HRMS: calcd for C10H12O2Na (M+Na)+ : 187.0730, found : 187.0731.

Formula: C10H12O2 MW = 164.20 g.mol–1

Formula: C10H12O2 MW = 164.20 g.mol–1

For both (E)- and (Z)-isomers:

HRMS: calcd for C11H15O3 (M+H)+ : 195.1016, found : 195.1017.

Formula: C11H14O3 MW = 194.23 g.mol–1

Formula: C11H14O3 MW = 194.23 g.mol–1

Formula: C11H15NO MW = 177.24 g.mol–1

Formula: C11H15NO MW = 177.24 g.mol–1

For both (E)- and (Z)-isomers:

The description of (Z)-1g from the mixture is reported.

Compound 1h was synthesized from 4-(diethylamino)-2-methoxybenzaldehyde (0.518 mg, 2.50

For both (E)- and (Z)-isomers:

HRMS: calcd for C14H22NO2 (M+H)+ : 236.1645, found : 236.1643.

Formula: C14H21NO2 MW = 235.32 g.mol–1

Formula: C14H21NO2 MW = 235.32 g.mol–1

For both (E)- and (Z)-isomers:

Formula: C8H9NO MW = 135.16 g.mol–1

Formula: C8H9NO MW = 135.16 g.mol–1

Compound 1j was synthesized from 1-methylindole-3-carboxaldehyde (821 mg, 5.00 mmol)

For both (E)- and (Z)-isomers:

Formula: C12H13NO MW = 187.24 g.mol–1

Formula: C12H13NO MW = 187.24 g.mol–1

Compound 1k was synthesized from N-methylpyrrole-2-carboxaldehyde (557 mg, 5.00 mmol)

For both (E)- and (Z)-isomers:

HRMS: calcd for C8H12ON (M+H)+ : 138.0913, found : 138.0910.

Formula: C8H11NO MW = 137.18 g.mol–1

Formula: C8H11NO MW = 137.18 g.mol–1

For both (E)- and (Z)-isomers:

Formula: C7H8O2 MW = 124.14 g.mol–1

Formula: C7H8O2 MW = 124.14 g.mol–1

For both (E)- and (Z)-isomers:

Formula: C7H8OS MW = 140.20 g.mol–1

Formula: C7H8OS MW = 140.20 g.mol–1

Formula: C12H24O MW = 184.32 g.mol–1