Total synthesis of the Strychnos alkaloids (±)-akuammicine and (±)-norfluorocurarine from 3a-(o-nitrophenyl)hexahydroindol-4-ones by nickel(0)-promoted double cyclization

Journal of Organic Chemistry

Volumn 61, Issue 13, 1996, Pages 4194-4195

  Solé, Daniel ^a   Bonjoch, Josep ^a   Bosch, Joan ^a  

^a UNIVERSITY OF BARCELONA   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

AKUAMMICINE; ALKALOID; NORFLUOROCURARINE; UNCLASSIFIED DRUG;

ARTICLE; DRUG SYNTHESIS; PHOTOCHEMISTRY; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0030036498     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo960588l     Document Type: Article

References (30)

1. For recent reviews, see: (a) Sapi, J.; Massiot, G. Monoterpenoid Indole Alkaloids; Saxton, J. E., Ed. In The Chemistry of Heterocyclic Compounds; Taylor, E. C., Ed.; Wiley: New York, 1994; Suppl. to Vol. 25, Part 4, pp 279-355. (b) Bosch, J.; Bonjoch, J.; Amat, M. In The Alkaloids; Cordell, G. A., Ed.; Academic Press: New York, 1996; Vol. 48, pp 75-189.
2. For recent reviews, see: (a) Sapi, J.; Massiot, G. Monoterpenoid Indole Alkaloids; Saxton, J. E., Ed. In The Chemistry of Heterocyclic Compounds; Taylor, E. C., Ed.; Wiley: New York, 1994; Suppl. to Vol. 25, Part 4, pp 279-355. (b) Bosch, J.; Bonjoch, J.; Amat, M. In The Alkaloids; Cordell, G. A., Ed.; Academic Press: New York, 1996; Vol. 48, pp 75-189.
3. Bonjoch, J.; Solé, D.; Bosch, J. J. Am. Chem. Soc. 1993, 115, 2064-2065.
4. Angle, S. R.; Fevig, J. M.; Knight, S. D.; Marquis, R. W., Jr.; Overman, L. E. J. Am. Chem. Soc. 1993, 115, 3966-3977.
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6. Bonjoch, J.; Solé, D.; Bosch, J. J. Am. Chem. Soc. 1995, 117, 11017-11018.
7. 2 in cyclizations of vinyl halides with alkenes, see: Solé, D.; Cancho, Y.; Llebaria, A.; Moretó, J. M.; Delgado, A. J. Am. Chem. Soc. 1994, 116, 12133-12134.
8. The biogenetic numbering and ring labeling is used throughout this paper: Le Men, J.; Taylor, W. I. Experientia 1965, 21, 508-510.
9. 13C NMR, and/or microanalysis.
10. (a) For the isolation of (±)-akuammicine, see: Edwards, P. N.; Smith, G. F. Proc. Chem. Soc. (London) 1960, 215.
11. (b) For previous syntheses of this racemic alkaloid, see: Kuehne, M. E.; Xu, F.; Brook, C. S. J. Org. Chem. 1994, 59, 7803-7806. See also ref 3.
12. For the use of this photoisomerization in the synthesis of Strychnos alkaloids, see: (a) Amat, M.; Linares, A.; Bosch, J. J. Org. Chem. 1990, 55, 6299-6312. (b) Gràcia, J.; Casamitjana, N.; Bonjoch, J.; Bosch, J. J. Org. Chem. 1994, 59, 3939-3951. For the use of this process in the construction of the anilinoacrylate moiety present in other groups of indole alkaloids, see: (c) Overman, L. E.; Sworin, M.; Burk, R. M. J. Org. Chem. 1983, 48, 2685-2690. (d) Wenkert, E.; Porter, B.; Simmons, D. P. J. Org. Chem. 1984, 49, 3733-3742.
13. For the use of this photoisomerization in the synthesis of Strychnos alkaloids, see: (a) Amat, M.; Linares, A.; Bosch, J. J. Org. Chem. 1990, 55, 6299-6312. (b) Gràcia, J.; Casamitjana, N.; Bonjoch, J.; Bosch, J. J. Org. Chem. 1994, 59, 3939-3951. For the use of this process in the construction of the anilinoacrylate moiety present in other groups of indole alkaloids, see: (c) Overman, L. E.; Sworin, M.; Burk, R. M. J. Org. Chem. 1983, 48, 2685-2690. (d) Wenkert, E.; Porter, B.; Simmons, D. P. J. Org. Chem. 1984, 49, 3733-3742.
14. For the use of this photoisomerization in the synthesis of Strychnos alkaloids, see: (a) Amat, M.; Linares, A.; Bosch, J. J. Org. Chem. 1990, 55, 6299-6312. (b) Gràcia, J.; Casamitjana, N.; Bonjoch, J.; Bosch, J. J. Org. Chem. 1994, 59, 3939-3951. For the use of this process in the construction of the anilinoacrylate moiety present in other groups of indole alkaloids, see: (c) Overman, L. E.; Sworin, M.; Burk, R. M. J. Org. Chem. 1983, 48, 2685-2690. (d) Wenkert, E.; Porter, B.; Simmons, D. P. J. Org. Chem. 1984, 49, 3733-3742.
15. For the use of this photoisomerization in the synthesis of Strychnos alkaloids, see: (a) Amat, M.; Linares, A.; Bosch, J. J. Org. Chem. 1990, 55, 6299-6312. (b) Gràcia, J.; Casamitjana, N.; Bonjoch, J.; Bosch, J. J. Org. Chem. 1994, 59, 3939-3951. For the use of this process in the construction of the anilinoacrylate moiety present in other groups of indole alkaloids, see: (c) Overman, L. E.; Sworin, M.; Burk, R. M. J. Org. Chem. 1983, 48, 2685-2690. (d) Wenkert, E.; Porter, B.; Simmons, D. P. J. Org. Chem. 1984, 49, 3733-3742.
16. Hu, W.-L.; Zhu, J.-P.; Hesse, M. Planta Med. 1989, 55, 463-466. See also ref 9b.
17. We are indebted to Professor Georges Massiot (University of Reims) for providing us with an authentic sample of natural akuammicine.
18. 3, DMF, 50-60°C) of dehydrotubifoline 3 to the N-formyl derivative 5 has been previously reported (no yield indicated): see ref 3.
19. Lenz, G. R. Synthesis 1978, 489-518.
20. (a) For the isolation of (±)-norfluorocurarine, see: Rakhimov, D. A.; Malikov, V. M.; Yusunov, C. Y. Khim. Prir. Soedin 1969, 5, 461-462; Chem. Abstr. 1970, 72, 67165n.
21. (a) For the isolation of (±)-norfluorocurarine, see: Rakhimov, D. A.; Malikov, V. M.; Yusunov, C. Y. Khim. Prir. Soedin 1969, 5, 461-462; Chem. Abstr. 1970, 72, 67165n.
22. (b) For the only previous synthesis of this racemic alkaloid, see: Crawley, G. C.; Harley-Mason J. J. Chem. Soc., Chem. Commun. 1971, 685-686.
23. Clivio, P.; Richard, B.; Deverre, J.-R.; Sevenet, T.; Zeches, M.; Le Men-Oliver, L. Phytochemistry 1991, 30, 3785-3792.
24. 2O 292.1582, found 292.1577.
25. Atta-ur-Rahman; Habib-ur-Rehman; Ahmad, Y.; Fatima, K.; Badar, Y. Planta Med. 1987, 53, 256-259.
26. We thank Professor Atta-ur-Rahman for sending us detailed spectroscopic data of bharhingine.
27. For alkene isomerizations in intramolecular palladium-catalyzed vinylations of olefins, see: (a) Owezarczyk, Z.; Lamaty, F.; Vawter, E. J.; Negishi, E. J. Am. Chem. Soc. 1992, 114, 10091-10092. (b) Rawal, V. H.; Michoud, C. J. Org. Chem. 1993, 58, 5583-5584.
28. For alkene isomerizations in intramolecular palladium-catalyzed vinylations of olefins, see: (a) Owezarczyk, Z.; Lamaty, F.; Vawter, E. J.; Negishi, E. J. Am. Chem. Soc. 1992, 114, 10091-10092. (b) Rawal, V. H.; Michoud, C. J. Org. Chem. 1993, 58, 5583-5584.
29. Bosch, J.; Bennasar, M. L. Heterocycles 1983, 20, 2471-2511.
30. For a previous synthesis of 19,20-didehydrotubifolidine (9), see: Smith, G. F.; Wróbel, J. T. J. Chem. Soc. 1960, 792-795.