A Short, Enantioselective Synthesis of the AB-Ring Substructure of the Brevetoxins via endo-Selective Alkynol Cycloisomerization

Journal of Organic Chemistry

Volumn 62, Issue 18, 1997, Pages 6432-6435

  Gleason, Mark M ^a   McDonald, Frank E ^a  

^a NORTHWESTERN UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001608288     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo970597+     Document Type: Article

References (25)

1. (a) Catterall, W. A. Science 1988, 242, 50.
2. (b) Trainer, V. L.; Edwards, R. A.; Szmant, A. M.; Stuart, A. M.; Mende, T. J.; Baden, D. G. In Marine Toxins: Origin, Structure, and Molecular Pharmacology; Hall, S., Strichartz, G., Eds.; ACS Symposium Series 418; American Chemical Society: Washington, DC, 1990; pp 166-175.
3. (c) Shimizu, Y. Chem. Rev. 1993, 93, 1685.
4. (d) Garson, M. Chem. Rev. 1993, 93, 1699.
5. (e) Yasumoto, T.; Murata, M. Chem. Rev. 1993, 93, 1897.
6. (a) Alvarez, E.; Candenas, M.-L.; Pérez, R.; Ravelo, J. L.; Martín, J. D. Chem. Rev. 1995, 95, 1953.
7. (b) Nicolaou, K. C. Angew. Chem. Int. Ed. 1996, 35, 588.
8. For syntheses of hemibrevetoxin B, see: (c) Nicolaou, K. C.; Reddy, K. R.; Skokotas, G.; Sato, F.; Xiao, X.-Y.; Hwang, C.-K. J. Am. Chem. Soc. 1993, 115, 3558.
9. (d) Kadota, I.; Jung-Youl, P.; Koumura, N.; Pollaud, G.; Matsukawa, Y.; Yamamoto, Y. Tetrahedron Lett. 1995, 36, 5777.
10. (e) Morimoto, M.; Matsukura, H.; Nakata, T. Tetrahedron Lett. 1996, 37, 6365.
11. (f) Mori, Y.; Yaegashi, Y.; Furukawa, H. J. Am. Chem. Soc. 1997, 119, 4557.
12. Riediker, M.; Schwartz, J. J. Am. Chem. Soc. 1982, 104, 5842.
13. McDonald, F. E.; Bowman, J. L. Tetrahedron Lett. 1996, 37, 4675.
14. (a) Kanao, M.; Hashimuze, T.; Ichikawa, Y.; Irie, K.; Isoda, S. J. Med. Chem. 1982, 25, 1358.
15. (b) Baudouy, R.; Prince, P. Tetrahedron 1989, 45, 2067.
16. (a) Price, C. C.; Pappalardo, J. A. J. Am. Chem. Soc. 1950, 72, 2613.
17. (b) Paterson, I.; Smith, J. D.; Ward, R. A. Tetrahedron 1995, 51, 9413.
18. Mukaiyama, T. Angew. Chem. Int. Ed. Engl. 1977, 16, 817.
19. Jung, M. E.; Blum, R. B. Tetrahedron Lett. 1977, 18, 3791.
20. Luche, J.-L.; Gemal, A. L. J. Am. Chem. Soc. 1979, 101, 5848.
21. (a) Corey, E. J.; Fuchs, P. L. Tetrahedron Lett. 1972, 13, 3796.
22. (b) Romo, D.; Johnson, D. D.; Plamondon, L.; Miwa, T.; Schreiber, S. L. J. Org. Chem. 1992, 57, 5060.
23. (a) Shing, T. K. M.; Tai, V. W.-F.; Tam, E. K. W. Angew. Chem. Int. Ed. Engl. 1994, 33, 2312.
24. (b) Shing, T. K. M.; Tam, E. K. W.; Tai, V. W.-F.; Chung, I. H. F.; Jiang, Q. Chem. Eur. J. 1996, 2, 50.
25. We attribute the failure of this relatively general cyclization reaction to an unfavorable conformational equilibrium in compounds 16 and 17. Although conformation i chemical equation presented has the frarcs-diequatorial relationship of propargyl and hydroxyl substituents required for cyclization, a cis-1,3-diaxial interaction is present between the C4-hydroxyl group and the C6-side chain. This interaction is avoided in conformation ii, but now the C2-propargyl and C3-hydroxyl substituents are in a trans-diaxial configuration. The vlnylidene carbene arising from 16 apparently decomposes (possibly by an intermolecular reaction leading to polymerization) at a faster rate than the conformational interconversion required for cyclization.