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HETEROCYCLES, Vol. 68, No. 10, 2006
2.01-2.30 (m, 1H), 2.50-2.71 (m, 1H), 2.80-3.02 (m, 2H), 3.51-3.80 (br s, 1H), 3.90-4.21 (br s, 1H),
13
4.91-5.12 (m, 4H), 5.50-5.81 (m, 2H). C NMR (50.5 MHz, CDCl3): δ = 154.9 , 140.2, 132.0, 131.5,
116.2, 114.6, 114.5, 79.9, 79.8, 60.5, 60.4, 55.5, 52.3, 41.1, 40.2, 36.8, 28.9, 28.8. Anal. Calcd for
C13H21NO2: C, 69.92; H, 9.48; N, 6.27. Found: C, 69.75; H, 9.32; N, 6.12.
25
tert-Butyl (3S,5R)-(+)-2-oxo-3,5-divinylpyrrolidine-1-carboxylate [(+)-9a], pale yellow oil. [α]D
+4.0 (c = 0.7, CHCl3). IR (neat) 1780, 1730 cm-1. 1H NMR (200 MHz, CDCl3): δ = 1.44 (s, 9H), 2.07 (m,
13
2H), 3.21 (m, 1H), 4.58 (t, 1H), 5.16 (m, 4H), 5.84 (m, 2H). C RMN (50.5 MHz, CDCl3): δ = 174.0,
150.5, 136.6, 134.1, 118.4, 115.8, 83.2, 57.7, 45.6, 36.5, 28.4. Anal. Calcd for C13H19NO3: C, 65.80; H,
8.07; N, 5.90. Found: C, 65.67; H, 8.15; N, 5.78.
tert-Butyl (5R)-(-)-(3E)-3-ethylidene-2-oxo-5-vinylpyrrolidine-1-carboxylate [(-)-9b], pale yellow oil.
25
1
[α]D -13.0 (c = 1.8, CHCl3). IR (neat) 1775, 1712 cm-1. H NMR (200 MHz, CDCl3): δ = 1.44 (s, 9H),
1.73 (dt, 3H), 2.36 (br d, 1H), 2.78 (m, 1H), 4.57 (td., 1H), 5.09 (m, 2H), 5.71 (m, 1H), 6.70 (m, 1H ). 13C
NMR (50.5 MHz, CDCl3): δ = 166.6, 150.3, 137.9, 133.5, 130.7, 115.4, 82.7, 56.7, 28.6, 28.0, 14.8. Anal.
Calcd for C13H19NO3: C, 65.80; H, 8.07; N, 5.90. Found: C, 65.70; H, 8.00; N, 5.82.
Ethyl (±)-cis-1-(1-phenylethyl)-3,5-divinylpyrrolidine-2-carboxylate (10), colorless oil. IR (neat) 1725
1
cm-1. H NMR (200 MHz, CDCl3): δ = 1.22 (t, 3H, J=7.1Hz), 1.34 (d, 3H, J=6.7Hz), 1.48 (ddd, J=13.0,
4.2, 3.2), 2.55 (dt, 1H, J=13.0, 8.8 Hz), 2.66-2.76 (m, 1H), 3.54 (d, 1H, J=2.7 Hz), 3.93, (td, 1H, J=8.8,
4.3 Hz) 3.98 (q, 1H, J=6.7 Hz), 4.00 (q, 2H, J=7.1 Hz), 4.68-5.06 (m, 4H), 5.47-5.62 (m, 1H), .6.70-6.02
13
(m, 1H), 7.10-7.40 (m, 5H). C NMR (50.5 MHz, CDCl3): δ = 175.3, 145.1, 142.1, 142.0, 128.6, 128.1,
127.2, 114.4, 114.3, 68.3, 65.3, 60.6, 58.2, 46.5, 38.6, 20.2, 14.6. Anal. Calcd for C19H25NO2: C, 76.22; H,
8.42; N, 4.68. Found: C, 76.05; H, 8.30; N, 4.52.
Ethyl (±)-cis-1-tert-butoxycarbonyl-3,5-divinylpyrrolidine-2-carboxylate (11), colorless oil. IR (neat)
1772, 1739 cm-1. 1H NMR (200 MHz, CDCl3): δ = 1.24 (m, 3H), 1.34 (s, 9H), 1.56 (m, 1H), 2.22 (m, 1H),
2.76 (dd, 1H), 4.23 (m, 4H), 5.03 (m, 2H), 5.73 (m, 2H). 13C NMR (50.5 MHz, CDCl3): δ = 172.5, 140.2,
138.2, 116.0, 114.3, 80.2, 65.4, 60.9, 46.3, 38.0, 28.2. Anal. Calcd for C16H25NO4: C, 65.06; H, 8.53; N,
4.74. Found: C, 64.95; H, 8.42; N, 4.62.
REFERENCES
1. For recent general reviews, see: (a) S. J. Connon and S. Blechert, Angew. Chem. Int. Ed., 2003, 42,
1900. (b) R. H. Grubbs, T. M. Truka, and M. S. Sandford, Curr. Meth. Inorg. Chem., 2003, 3, 187.
(c) B. C. G. Soderberg, Coord. Chem. Rev., 2003, 241, 147. (d) A. Fürstner, Angew. Chem. Int. Ed.,
2000, 39, 3012.
2. For reviews on the use of norbornenes in ROM-CM sequences, see: (a) O. Arjona, A. G. Csákÿ, and