Synthesis of Polysubstituted Alkenes
FULL PAPER
2-(4-Methoxyphenyl)but-1-ene (27):[58] 1H NMR: δ ϭ 1.11 (t, J ϭ
Ethyl 2-(4-Fluorophenyl)acrylate (41):[70] 1H NMR: δ ϭ 1.32 (t, J ϭ
7.4 Hz, 3 H, Me), 2.48 (q, J ϭ 7.4 Hz, 2 H, CH2), 3.80 (s, 3 H, 7.0 Hz, 3 H, Me), 4.28 (q, J ϭ 7.0 Hz, 2 H, CH2), 5.85 (s, 1 H, ϭ
OMe), 4.98 (s, 1 H, ϭCHH), 5.21 (s, 1 H, ϭCHH), 6.85 (d, J ϭ CHH), 6.34 (s, 1 H, ϭCHH), 7.02 (t, J ϭ 8.6 Hz, 2 H, Ar), 7.38
8.8 Hz, 2 H, Ar), 7.37 (d, J ϭ 8.8 Hz, 2 H, Ar) ppm.
(dd, J ϭ 8.6, 5.5 Hz, 2 H, Ar) ppm.
Ethyl 2-(1-Naphthyl)acrylate (42):[71] 1H NMR: δ ϭ 1.19 (t, J ϭ
7.0 Hz, 3 H, Me), 4.20 (q, J ϭ 7.0 Hz, 2 H, CH2), 5.87 (s, 1 H, ϭ
CHH), 6.69 (s, 1 H, ϭCHH), 7.35 (dd, J ϭ 7.0, 1.1 Hz, 1 H, Ar),
7.45 (m, 3 H, Ar), 7.72 (m, 1 H, Ar), 7.84 (m, 2 H, Ar) ppm.
2-(2-Methoxyphenyl)but-1-ene (28):[59] 1H NMR: δ ϭ 1.11 (t, J ϭ
7.4 Hz, 3 H, Me), 2.57 (q, J ϭ 7.4 Hz, 2 H, CH2), 3.90 (s, 3 H,
OMe), 5.10 (d, J ϭ 1.5 Hz, 1 H, ϭCHH), 5.24 (d, J ϭ 1.5 Hz, 1
H, ϭCHH), 7.00 (m, 2 H, Ar), 7.23 (dd, J ϭ 7.5, 1.9 Hz, 1 H, Ar),
7.35 (m, 1 H, Ar) ppm.
Ethyl 2-(6-Methoxy-2-naphthyl)acrylate (43):[72] 1H NMR: δ ϭ 1.30
(t, J ϭ 7.0 Hz, 3 H, Me), 3.95 (s, 3 H, OMe), 4.32 (q, J ϭ 7.0 Hz,
2 H, CH2), 5.97 (s, 1 H, ϭCHH), 6.36 (s, 1 H, ϭCHH), 7.12 (m,
2 H, Ar), 7.49 (dd, J ϭ 8.4, 1.7 Hz, 1 H, Ar), 7.71 (m, 2 H, Ar),
7.83 (s, 1 H, Ar) ppm.
2-(4-Fluorophenyl)but-1-ene (29):[60] 1H NMR: δ ϭ 1.09 (t, J ϭ
7.4 Hz, 3 H, Me), 2.48 (q, J ϭ 7.4 Hz, 2 H, CH2), 5.04 (s, 1 H, ϭ
CHH), 5.22 (s, 1 H, ϭCHH), 7.00 (t, J ϭ 8.5 Hz, 2 H, Ar), 7.36
(dd, J ϭ 5.5, 8.5 Hz, 2 H, Ar) ppm.
Ethyl 2-[3,5-Bis(trifluoromethyl)phenyl]acrylate (44): 1H NMR: δ ϭ
1.32 (t, J ϭ 7.0 Hz, 3 H, Me), 4.31 (q, J ϭ 7.0 Hz, 2 H, CH2), 6.03
(s, 1 H, ϭCHH), 6.57 (s, 1 H, ϭCHH), 7.84 (s, 1 H, Ar), 7.88 (s,
2 H, Ar) ppm. C13H10F6O2 (312.2): calcd. C 50.01, H 3.23; found
C 50.18, H 3.10.
2-(2-Methylphenyl)but-1-ene (30):[61] 1H NMR: δ ϭ 1.02 (t, J ϭ
7.4 Hz, 3 H, Me), 2.31 (q, J ϭ 7.4 Hz, 2 H, CH2), 2.27 (s, 3 H,
Me), 4.83 (s, 1 H, ϭCHH), 5.15 (s, 1 H, ϭCHH), 7.00Ϫ7.30 (m, 4
H, Ar) ppm.
1-(4-Methoxyphenyl)-2-methylprop-1-ene (31):[62] 1H NMR: δ ϭ
1.84 (s, 3 H, Me), 1.87 (s, 3 H, Me), 3.80 (s, 3 H, OMe), 6.20 (s, 1
H, ϭCH), 6.85 (d, J ϭ 8.8 Hz, 2 H, Ar), 7.15 (d, J ϭ 8.8 Hz, 2 H,
Ar) ppm.
1
Ethyl 2-(4-N,N-Dimethylaminophenyl)acrylate (45): H NMR: δ ϭ
1.32 (t, J ϭ 7.0 Hz, 3 H, Me), 2.96 (s, 6 H, NMe2), 4.28 (q, J ϭ
7.0 Hz, 2 H, CH2), 5.76 (s, 1 H, ϭCHH), 6.12 (s, 1 H, ϭCHH),
6.68 (d, J ϭ 8.7 Hz, 2 H, Ar), 7.32 (d, J ϭ 8.7 Hz, 2 H, Ar) ppm.
C13H17NO2 (219.3): calcd. C 71.21, H 7.81; found C 70.98, H 7.62.
1-(2-Methoxyphenyl)-2-methylprop-1-ene (32):[63] 1H NMR: δ ϭ
1.80 (s, 3 H, Me), 1.92 (s, 3 H, Me), 3.82 (s, 3 H, OMe), 6.30 (s, 1
H, ϭCH), 6.85 (d, J ϭ 8.7 Hz, 1 H, Ar), 6.91 (t, J ϭ 7.5 Hz, 1 H,
Ar), 7.17 (m, 2 H, Ar) ppm.
General Procedure for the Coupling of Aryl Bromides and Alkenes:
The reaction of the aryl bromide (10 mmol), K2CO3 (2.76 g,
20 mmol) and the alkene (13 mmol) in the presence of the Tedicyp-
palladium complex, at 130 °C for 20 h in anhydrous DMF (10 mL)
under argon, affords the corresponding addition product after ad-
dition of water, extraction with dichloromethane, separation, dry-
ing (MgSO4), evaporation and filtration through silica gel.
2-Methyl-1-naphthylprop-1-ene (33):[64] 1H NMR: δ ϭ 1.74 (s, 3 H,
Me), 2.04 (s, 3 H, Me), 6.68 (s, 1 H, ϭCH), 7.30 (d, J ϭ 7.0 Hz, 1
H, Ar), 7.48Ϫ8.05 (m, 6 H, Ar) ppm.
3-Methyl-2-phenylbut-2-ene (34):[65] 1H NMR: δ ϭ 1.48 (s, 3 H,
Me), 1.70 (s, 3 H, Me), 1.85 (s, 3 H, Me), 7.00 (d, J ϭ 6.8 Hz, 2
H, Ar), 7.10Ϫ7.25 (m, 3 H, Ar) ppm.
1-(4-Methoxyphenyl)-1,2-diphenylethylene (16):[73] 1H NMR, (Z)
isomer: δ ϭ 3.84 (s, 3 H, OMe), 6.83Ϫ7.36 (m, 15 H) ppm; (E)
isomer: δ ϭ 3.82 (s, 3 H, OMe), 6.83Ϫ7.36 (m, 15 H) ppm.
2-(4-Methoxyphenyl)-3-methylbut-2-ene (35):[66] 1H NMR: δ ϭ 1.60
(s, 3 H, Me), 1.79 (s, 3 H, Me), 1.94 (s, 3 H, Me), 3.80 (s, 3 H,
OMe), 6.84 (d, J ϭ 8.7 Hz, 2 H, Ar), 7.04 (d, J ϭ 8.7 Hz, 2 H,
Ar) ppm.
1,1-Diphenyl-2-(3-trifluoromethylphenyl)ethylene (17):[74] 1H NMR:
δ ϭ 6.89 (s, 1 H, ϭCH), 7.05Ϫ7.32 (m, 14 H, Ar) ppm. MS (EI,
70 eV): m/z (%) ϭ 324 (100) [Mϩ].
2-(4-Fluorophenyl)-3-methylbut-2-ene (36):[67] 1H NMR: δ ϭ 1.57
(s, 3 H, Me), 1.79 (s, 3 H, Me), 1.93 (s, 3 H, Me), 6.92Ϫ7.10 (m, 4
H, Ar) ppm.
1,1-Diphenyl-2-(4-trifluoromethylphenyl)ethylene (18): 1H NMR:
δ ϭ 6.98 (s, 1 H, ϭCH), 7.11 (d, J ϭ 8.3 Hz, 2 H, Ar), 7.15Ϫ7.40
(m, 12 H, Ar) ppm. C21H15F3 (324.3): calcd. C 77.77, H 4.66; found
C 77.89, H 4.87. MS (EI, 70 eV): m/z (%) ϭ 324 (100) [Mϩ].
Ethyl 2-Phenylacrylate (37):[68] 1H NMR: δ ϭ 1.32 (t, J ϭ 7.1 Hz,
3 H, Me), 4.27 (q, J ϭ 7.1 Hz, 2 H, CH2), 5.88 (s, 1 H, ϭCHH),
6.34 (s, 1 H, ϭCHH), 7.26Ϫ7.50 (m, 5 H, Ph) ppm.
1,1-Diphenyl-2-(4-methoxyphenyl)ethylene (19):[75] 1H NMR: δ ϭ
3.74 (s, 3 H, OMe), 6.66 (d, J ϭ 8.7 Hz, 2 H, Ar), 6.94 (m, 3 H, ϭ
CH and Ar), 7.17Ϫ7.35 (m, 10 H, Ar) ppm.
Ethyl 2-(2-Methylphenyl)acrylate (38):[68] 1H NMR: δ ϭ 1.29 (t,
J ϭ 7.1 Hz, 3 H, Me), 2.21 (s, 3 H, Me), 4.25 (q, J ϭ 7.1 Hz, 2 H,
CH2), 5.70 (s, 1 H, ϭCHH), 6.50 (s, 1 H, ϭCHH), 7.00Ϫ7.35 (m,
4 H, Ar) ppm.
1,1-Diphenyl-2-(4-fluorophenyl)ethylene (20):[76] 1H NMR: δ ϭ 6.81
(t, J ϭ 8.8 Hz, 2 H, Ar), 6.91 (s, 1 H, ϭCH), 6.97 (dd, J ϭ 5.7,
8.8 Hz, 2 H, Ar), 7.17 (m, 2 H, Ph), 7.25Ϫ7.35 (m, 8 H, Ph) ppm.
Ethyl 2-(2-Methoxyphenyl)acrylate (39):[69] 1H NMR: δ ϭ 1.25 (t,
J ϭ 7.0 Hz, 3 H, Me), 3.78 (s, 3 H, MeO), 4.25 (q, J ϭ 7.0 Hz, 2
H, CH2), 5.72 (d, J ϭ 1.5 Hz, 1 H, ϭCHH), 6.26 (d, J ϭ 1.5 Hz,
1 H, ϭCHH), 6.87 (d, J ϭ 8.3 Hz, 1 H, Ar), 6.65 (t, J ϭ 7.5 Hz,
1 H, Ar), 7.22 (d, J ϭ 7.5 Hz, 1 H, Ar), 7.32 (t, J ϭ 7.3 Hz, 1 H,
Ar) ppm.
Acknowledgments
´ ´
We thank the CNRS and the ‘‘Conseil General des
ˆ
BouchesϪduϪRhone, Fr’’ for providing financial support.
[1]
N. Withcombe, K. K. Hii, S. Gibson, Tetrahedron 2001, 57,
Ethyl 2-(4-Methoxyphenyl)acrylate (40):[68] 1H NMR: δ ϭ 1.30 (t,
J ϭ 7.0 Hz, 3 H, Me), 3.81 (s, 3 H, MeO), 4.27 (q, J ϭ 7.0 Hz, 2
H, CH2), 5.82 (s, 1 H, ϭCHH), 6.26 (s, 1 H, ϭCHH), 6.87 (d, J ϭ
8.5 Hz, 2 H, Ar), 7.36 (d, J ϭ 8.5 Hz, 2 H, Ar) ppm.
7449Ϫ7476.
[2]
I. Beletskaya, A. Cheprakov, Chem. Rev. 2000, 100,
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A. Suzuki, J. Organomet. Chem. 2002, 653, 83Ϫ90.
[3]
Eur. J. Org. Chem. 2003, 1091Ϫ1096
1095