2062
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18. Fogg, D. F.; dos Santos, F. N. Coord. Chem. Rev. 2004,
248, 2365–2379.
19. (a) Pelissier, H. Tetrahedron 2006, 62, 1619–1665; (b)
Pelissier, H. Tetrahedron 2006, 62, 2143–2173.
20. Nicolaou, K. C.; Edmonds, D. J.; Bulger, P. G. Angew.
Chem., Int. Ed. 2006, 45, 7134–7186.
21. (a) Kim, B. G.; Snapper, M. L. J. Am. Chem. Soc. 2006,
128, 52–53; (b) Eckert, M.; Monnier, F.; Shchetnikov, G.
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14H), 2.19 (t, J = 7.5 Hz, 2H), 2.82 (t, J = 7.0 Hz, 2H),
3.53 (dt, J = 6.5 and 7.0 Hz, 2H), 5.35–5.50 (m, N–H),
7.18–7.35 (m, 5H). 13C NMR (CDCl3, 75 MHz): trans-2:
d = 12.06, 14.4, 18.5, 19.2, 22.9, 29.6, 29.7, 29.9, 30.7, 32.2,
34.4, 36.0, 37.1, 40.8, 126.7, 128.9, 129.0, 139.2, 173.3.
Compound 20 (mixture of cis and trans-isomers): 1H
NMR (CDCl3, 300 MHz): d = ꢀ0.05–0.06 (m, 0.45H cis-
isomer), 0.15–0.25 (m, 1.55H, trans-isomer), 0.30–0.55 (m,
2H), 0.81 (t, J = 6.2 Hz, 3H), 1.97 (dd, J = 7.3 and
16.2 Hz, 1H), 2.09 (dd, J = 6.8 and 16.2 Hz, 1H), 2.75 (t,
J = 6.8 Hz, 2H), 3.48 (dt, J = 6.6 and 6.4 Hz, 2H), 5.48–
5.60 (N–H, 0.22H cis-isomer), 5.80–6.00 (N–H, 0.78H
trans-isomer), 7.10–7.35 (m, 5H). MS: 302 (M+Å), 288, 232.
22. (a) Bruneau, C. Angew. Chem., Int. Ed. 2005, 44, 2328–
2334; (b) Peppers, B. P.; Diver, S. T. J. Am. Chem. Soc.
2004, 126, 9524–9525; Dragutan, V.; Dragutan, I. J.
Organomet. Chem. 2006, 691, 5129–5147.
1
Compound 12: H NMR (CDCl3, 300 MHz): d = 0.88 (t,
23. Typical procedure for the tandem reaction:
J = 6.8 Hz, 3H), 1.10–1.15 (m, 2H), 1.20–1.50 (m, 12H),
1.60–1.77 (m, 1H), 1.90–2.07 (m, 1H), 2.19–2.40 (m, 2H),
2.83 (t, J = 7.0 Hz, 2H), 3.53 (dt, J = 6.0 and 6.8 Hz, 2H),
5.40–5.55 (N–H), 7.10–7.40 (m, 5H). 13C NMR (CDCl3,
75 MHz): trans-12: d = 14.4, 22.9, 28.5, 29.5, 29.6, 32.1,
32.8, 35.2, 35.9, 36.2, 37.4, 38.6, 40.9, 126.8, 129.1, 131.9,
172.1. MS = 476, 474, 472 (M+Å), 394, 316, 274.
25. Inanaga, I.; Hirata, K.; Saeki, H.; Katsuki, T.; Yama-
guchi, M. Bull. Chem. Soc. Jpn. 1979, 52, 1989–1993.
26. Song, S. H.; Sanders, D. P.; Lee, C. W.; Grubbs, R. H.
J. Am. Chem. Soc. 2005, 127, 17160–17161.
27. Fedorynski, M. Chem. Rev. 2003, 103, 1099–1132.
28. (a) Maeda, H.; Hirai, T.; Sugimoto, A.; Mizuno, K. J.
Org. Chem. 2003, 68, 7700–7706; (b) Laurent, A.; Villalva-
Servin, N. P.; Forgione, P.; Wilson, P. D.; Smil, D. V.;
Fallis, A. G. Can. J. Chem. 2004, 82, 215–226.
A solution of vinyl acetic acid (0.086 g, 1 mmol) and octene
(0.561 g, 5 mmol) in dichloromethane (20 mL) was bub-
bled with a stream of dry nitrogen. Grubbs type II catalyst
(21.2 mg, 0.025 mmol) was next added and the resulting
solution was heated for 12 h. After a second addition of the
same amount of catalyst, the reaction was heated for an
additional 12 h. Diethylzinc (1.23 g, 10 mmol) was intro-
duced at 0 ꢁC by canula. After stirring for 5 min at this
temperature, diiodomethane (4.28 g, 16 mmol) was added.
After stirring 5 h at rt, the mixture was treated with a 10%
HCl aqueous solution, washed successively with a satu-
rated NaHCO3 solution and brine. The organic layers were
dried over MgSO4, filtered off and concentrated under
vacuum. Cyclopropane 1 and 10 were obtained in a 88/12
trans/cis ratio and 90% cumulative yield.
1
24. All new compounds were characterized by H, 13C NMR
29. Edlin, C. D.; Faulkner, J.; Quayle, P. Tetrahedron Lett.
2006, 47, 1145–1151.
30. Seigal, B. A.; Fajardo, C.; Snapper, M. L. J. Am. Chem.
Soc. 2005, 127, 16329–16332.
31. Schmidt, B.; Pohler, M. J. Organomet. Chem. 2005, 690,
5552–5555.
and mass spectroscopy.
Grenadamide 2 and its cis-isomer (mixture of isomers): 1H
NMR (CDCl3, 300 MHz): d = 0.11–0.23 (m, 1.7H, trans-
isomer), 0.30–0.47 (m, 1.7H, trans-isomer), 0.50–0.63 (m,
0.6H, cis-isomer), 0.87 (t, J = 7.0 Hz, 3H), 1.05–1.70 (m,