HECK/WITTIG REACTION COMBINATION
3205
tert-Butyl 2-(2-(E)-Acetylethenyl)-(E)-cinnamate (7b)
Yield 63%, colorless oil; nmax(neat)=cmꢂ1 3060, 2976, 2930, 1705, 1675, 1634,
1611, 1476, 1391, 1367, 1322, 1256, 1217, 975, 870, 761; dH(270 MHz, CDCl3) 1.55
(s, 9H, But), 2.41 (s, 3H, CH3), 6.29 (d, 1H, 3J 15.7), 6.61 (d, 1H, 3J 16.2), 7.40 (m, 2H),
3
3
7.57 (m, 2H), 7.88 (d, 1H, J 16.2), 7.94 (d, 1H, J 15.7); dC(67.8 MHz, CDCl3) 27.85
(CH3), 28.47 [3C, C(CH3)3], 81.21, 124.18, 127.86, 127.94, 130.16, 130.47, 130.71,
134.43, 134.93, 140.32, 140.40, 166.01, 198.45; m=z (EI, 70 eV) 272.1414 (Mþ C17H20O3
requires 272.1412), 272 (Mþ, 0.6), 216 (15), 198 (14), 173 (33), 157 (45), 128 (100).
Methyl-3-[5-(3-oxo-3-phenyl-(E)-propenyl)-thien-2-yl]-(E)-acrylate (9a)
Yield 55%, yellow solid, mp 115–117 ꢀC (found: C, 68.44; H, 4.73; C17H14O3S
requires C, 68.53; H, 4.73%); nmax(KBr)=cmꢂ1 3083, 2946, 2847, 1698, 1647, 1617,
1585, 1573, 1439, 1338, 1317, 1277, 1174, 1040, 1013, 964, 813, 778, 697, 653, and
507; dH(270 MHz; CDCl3; Me4Si) 3.81 (s, 3 H), 6.29 (d, 1 H, J 15.7), 7.22 (d, 1 H,
J 3.8), 7.28 (d, 1 H, J 3.8), 7.35 (d, 1 H, J 15.4), 7.46–7.65 (m, 3 H), 7.74 (d, 1 H, J
15.7), 7.87 (d, 1 H, J 15.3), and 8.00–8.10 (m, 2 H); dC(67.8 MHz; CDCl3; Me4Si)
51.8 (þ), 118.5 (þ), 122.3 (þ), 128.5 (þ), 128.8 (þ), 131.9 (þ), 132.8 (þ), 133.1 (þ),
136.3 (þ), 136.6 (þ), 138.0 (o), 142.1 (o), 142.8 (o), 167.0 (o), and 189.6 (o); m=z
(EI) 298.0669 (Mþ C17H14O3S requires 298.0664), 298 (25%), 77 (9), and 58 (100).
tert-Butyl 3-[5-(3-Oxo-(E)-but-1-enyl)-thien-2-yl]-(E)-acrylate (9b)
Yield 56%, orange oil; nmax(KBr)=cmꢂ1 2976, 2930, 1703, 1668, 1622, 1593,
1367, 1311, 1285, 1254, 1148, 967, 854, 804, 552, and 504; dH(270 MHz; CDCl3;
Me4Si) 1.53 (s, 9 H), 2.35 (s, 3H), 6.21 (d, 1 H, J 15.7), 6.53 (d, 1 H, J 15.9), 7.16
(d, 1 H, J 3.8), 7.21 (d, 1 H, J 3.8), 7.55 (d, 1 H, J 15.9), 7.61 (d, 1 H, J 15.7);
dC(67.8 MHz; CDCl3; Me4Si) 28.0 (þ), 80.9 (o), 121.2 (þ), 126.9 (þ), 131.3 (þ),
132.3 (þ), 135.0 (þ), 135.3 (þ), 141.7 (o), 142.7 (o), 165.8 (o), 197.6 (o); m=z (EI)
278.0979 (Mþ C15H18O3S requires 278.0977), 278 (20), 222 (62), 207 (100), 205
(21), 177 (11), and 134 (8).
Methyl-3-[5-(3-oxo-3-phenyl-(E)-propenyl)-fur-2-yl]-(E)-acrylate (9c). Yield
55%, yellow solid, mp 144–145 ꢀC (found: C, 71.71; H, 5.07; C17H14O4 ꢃ 0.1 H2O
requires C, 71.87; H, 5.04%); nmax(KBr)=cmꢂ1 3102, 2944, 2844, 1712, 1654, 1634,
1598, 1575, 1437, 1384, 1301, 1227, 1208, 1168, 1019, 970, 806, 779, 704, 636, and
501; dH(270 MHz; CDCl3; Me4Si) 3.82 (s, 3 H), 6.52 (d, 1 H, J 15.7), 6.70 (d, 1 H,
J 3.6), 6.76 (d, 1 H, J 3.6), 7.44 (d, 1 H, J 15.8), 7.48–7.65 (m, 5 H), and 8.00–8.10
(m, 2 H); dC(67.8 MHz; CDCl3; Me4Si) 51.8 (þ), 117.2 (þ), 117.8 (þ), 118.2 (þ),
121.1 (þ), 128.5 (þ), 128.8 (þ), 129.7 (þ), 130.4 (þ), 133.1 (þ), 138.0 (o), 152.7 (o),
153.4 (o), 167.2 (o), and 189.6 (o); m=z (EI) 282.0890 (Mþ C17H14O4 requires
282.0892), 282 (100%), 267 (7), 251 (15), 223 (29), 197 (28), 105 (47), and 77 (27).
(E,E)-5-[2-Benzoylethenyl]-2-styryl Furan (9d)
Yield 60%, orange solid, mp 108 ꢀC (from hexane=cyclohexane) (found: C,
83.59; H, 5.46; C21H16O2 ꢃ 0.1H2O requires C, 83.47; H, 5.40%); nmax(KBr)=cmꢂ1