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92%).
1 H NMR (300 MHz, CDCl3): δ 7.30-7.22 (m, 3H), 7.11-7.08 (m, 2H), 6.30 (dd, J = 17.2, 10.7
Hz, 1H), 6.15 (bs, 1H), 6.13 (q, J = 7.5 Hz, 1H), 6.00 (s, 1H), 5.49 (dd, J = 17.2, 1.5 Hz, 1H),
5.25 (dd, J = 10.8, 1.4 Hz, 1H), 3.77 (s, 3H), 3.21 (d, J = 13.1 Hz, 1H), 2.97 (d, J = 13.1 Hz, 1H),
2.16 (d, J = 7.4 Hz, 3H); 13 C NMR (75 MHz, CDCl3): δ 171.7, 164.9, 139.2, 138.7, 134.1, 133.9,
130.8, 128.7, 127.8, 126.1, 119.7, 118.5, 64.8, 53.3, 47.9, 16.3; IR (thin film): ν 3206, 2952,
2029, 1739, 1674, 1241 cm -1 ; MS m/z (%) 297 (25), 238 (40), 206 (100), 174 (77), 146 (71), 91
(83); EI-HRMS calcd for C18H19NO3 m/z [M] + 297.1365; found 297.1375.
HN
Bn
MeO2C O
146b
Methyl 2-benzyl-1,2,5,6-tetrahydro-5-methylene-6-oxo-4-vinylpyridine-2-carboxylate
(146b). Prepared by following general procedure H, using: 145b (20 mg, 78 µmol),
[Rh(CO)2Cl]2 (3.0 mg, 7.8 µmol). Reaction time 2 h. Yield 145b (10 mg, 45%).
1 H NMR (300 MHz, CDCl3): δ 7.40-7.36 (m, 3H), 7.21-7.15 (m, 2H), 6.49 (ddd, J = 17.2, 10.9,
1.0 Hz, 1H), 6.39 (s, 1H), 6.24 (s, 1H), 5.65 (d, J = 0.8 Hz, 1H), 5.64 (dd, J = 17.2, 1.5 Hz, 1H),
5.39 (dd, J = 10.8, 1.4 Hz, 1H), 3.84 (s, 3H), 3.38 (d, J = 13.2 Hz, 1H), 3.07 (d, J = 13.2 Hz, 1H);
13 C NMR (75 MHz, CDCl3): δ 170.9, 163.0, 135.6, 133.3, 132.6, 132.1, 130.3, 128.6, 127.6,
121.8, 121.3, 118.4, 64.6, 53.1, 47.6; IR (thin film): ν 3215, 2952, 1738, 1679, 1234 cm -1 .
HN
Bn
MeO2C (5Z)-Methyl-2-benzyl-1,2,5,6-tetrahydro-5-((trimethylsilyl)methylene)-6-oxo-4-vinyl-
O
146c
pyridine-2-carboxylate (146c). Prepared by following general procedure H, using: 145c (40
206
TMS