A biomimetic approach to the Strychnos alkaloids. A novel, concise synthesis of (±)-akuammicine and a route to (±)-strychnine

Journal of the American Chemical Society

Volumn 118, Issue 40, 1996, Pages 9804-9805

  Martin, Stephen F ^a   Clark, Cameron W ^a   Ito, Masayuki ^a   Mortimore, Michael ^a  

^a UNIVERSITY OF TEXAS AT AUSTIN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AKUAMMICINE; STRYCHNINE;

ARTICLE; DRUG SYNTHESIS; REACTION ANALYSIS;

EID: 0029909445     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja962577f     Document Type: Article

References (41)

1. Robinson, R. Experientia 1946, 2, 28.
2. (a) Millson, P.; Robinson, R.; Thomas, A. F. Experientia 1953, 9, 89.
3. (b) Edwards, P. N.; Smith, G. F. J. Chem. Soc. 1961, 152.
4. For representative synthetic efforts toward Strychnos alkaloids, see: (a) van Tamelen, E. E.; Dolby, L. J.; Lawton, R. G. Tetrahedron Lett. 1960, 30.
5. (b) Harley-Mason, J. Pure Appl. Chem. 1975, 41, 167.
6. (c) Takano, S.; Hirama, M.; Ogasawara, K. Tetrahedron Lett. 1982, 23, 881.
7. (d) Belgacem, L.; Henin, J.; Massiot, G.; Vercauteren, J. Tetrahedron Lett. 1987, 28, 3573.
8. (e) Bosch, J.; Bonjoch, J. In Studies in Natural Products Chemistry; Attaur-Rahman, Ed.; Elsevier: Amsterdam, 1988; Vol. 1, p 31.
9. (f) Nkiliza, J.; Vercautern, J.; Léger, J.-M. Tetrahedron Lett. 1991, 32, 1787.
10. (g) Amat, M.; Linares, A.; Bosch, J. J. Org. Chem. 1990, 55, 6299.
11. (h) Bonjoch, J.; Sole, D.; Bosch, J. J. Am. Chem. Soc. 1993, 115, 2064.
12. (i) Rawal, V. H.; Michoud, C.; Monestel, R. F.; J. Am, Chem. Soc. 1993, 115, 3030.
13. (j) Diez, A.; Vila, C.; Sinibaldi, M.-E.; Troin, Y.; Rubiralta, M. Tetrahedron Lett. 1993, 34, 733.
14. (k) Kraus, G. A.; Bougie, D. Tetrahedron 1994, 50, 2681.
15. (l) Bonjoch, J.; Sole, D.; Bosch, J. J. Am. Chem. Soc. 1995, 117, 11 017.
16. (a) Woodward, R. B.; Cava, M. P.; Ollis, W. D.; Hunger, A.; Daeniker, H. U.; Schenker, K. J. Am. Chem. Soc. 1954, 76, 4749.
17. (b) Woodward, R. B.; Cava, M. P.; Ollis, W. D.; Hunger, A.; Daeniker, H. U.; Schenker, K. Tetrahedron 1963, 19, 247.
18. (a) Magnus, P.; Giles, M.; Bonnert, R.; Kim, C. S.; McQuire, L.; Merritt, A.; Vicker, N. J. Am. Chem. Soc. 1992, 114, 4403.
19. (b) Magnus, P.; Giles, M.; Bonnert, R.; Johnson, G.; McQuire, L.; Deluca, M.; Merritt, A.; Kim, C. S.; Vicker, N. J. Am. Chem. Soc. 1993, 115, 8116.
20. Stork, G. Reported at the Ischia Advanced Scool of Organic Chemistry, Ischia Porto, Italy, September 21, 1992.
21. Knight, S. D.; Overman, L. E.; Pairaudeau, G. J. Am. Chem. Soc. 1993, 115, 9293.
22. Kuehne, M. E.; Xu, F. J. Org. Chem. 1993, 58, 7490.
23. Rawal, V. H.; Iwasa, S. J. Org. Chem. 1994, 59, 2685.
24. For a review of more recent applications of this concept, see: Trost, B. M. Science 1991, 254, 1471.
25. Angle, S. R.; Fevig, J. M.; Knight, S. D.; Marquis, R. W., Jr.; Overman, L. E. J. Am. Chem. Soc. 1993, 115, 3966.
26. Kuehne, M. E.; Xu, F.; Brook, C. S. J. Org. Chem. 1994, 59, 7803.
27. (a) Sole, D.; Bonjoch, J.; Bosch, J. J. Org. Chem. 1996, 61, 4194.
28. (b) Sole, D.; Bonjoch, J.; Garcia-Rubio, S.; Suriol, R.; Bosch, J. Tetrahedron Lett. 1996, 37, 5213.
29. (a) Wenkert, E.; Wickberg, B. J. Am. Chem. Soc. 1965, 87, 1580.
30. (b) Battersby, A. R.; Hall, E. S. J. Chem. Soc., Chem. Commun. 1969, 793.
31. (c) Scott, A. L.; Cherry, P. C.; Qureshi, A. A. J. Am. Chem. Soc. 1969, 91, 4932.
32. (d) Heimberger, S. L.; Scott, A. I. J. Chem. Soc., Chem. Commun. 1973, 217.
33. (e) Rahman, A.-ur; Basha, A. Biosynthesis of Indole Alkaloids; Clarendon Press: Oxford, 1983; p 45.
34. Martin, S. F.; Benage, B.; Geraci, L. S.; Hunter, J. E.; Mortimore, M. P. J. Am. Chem. Soc. 1991, 113, 6161 and references therein.
35. Ishii, Y.; Osakada, K.; Ikariya, T.; Saburi, M.; Yoshikawa, S. Tetrahedron Lett. 1983, 24, 2677.
36. We thank Professor Larry E. Overman (University of California, Irvine) for supplying a generous sample of authentic (±)-akuammicine (2).
37. Martin, S. F.; Mortimore, M. Tetrahedron Lett. 1990, 31, 4557 and references therein. Also, see: ref 15.
38. For example, see: (a) Vercauteren, J.; Massiot, G.; Levy, J. J. Org. Chem. 1984, 49, 3230.
39. (b) Feldman, P. L.; Rapoport, H. J. Am. Chem. Soc. 1987, 109, 1603.
40. Ahmad, Y.; Fatima, K.; Rahman, A.; Occolowitz, J. L.; Solheim, B. A.; Clardy, J.; Garnick, R. L.; Le Quesne, P. W. J. Am. Chem. Soc. 1977, 99, 1943.
41. As evidenced by following the course of the rearrangement by TLC, it appears that only one of the diastereoisomeric chloroindolenines 12a,b undergoes the rearrangement with the other remaining unchanged during the course of the reaction. This observation suggests that if the stereochemistry of the chlorination step could be controlled, the overall efficiency of this biomimetic conversion might be significantly improved.