An enantioselective synthesis of the Strychnos alkaloid (-)-tubifoline

Tetrahedron Asymmetry

Volumn 7, Issue 10, 1996, Pages 2775-2778

  Amat, Mercedes ^a   Coll, Ma Dolors ^a   Passarella, Daniele ^a   Bosch, Joan ^a  

^a UNIVERSITY OF BARCELONA   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

ALKALOID; TUBIFOLINE; UNCLASSIFIED DRUG;

ARTICLE; DRUG PURIFICATION; DRUG SYNTHESIS; ENANTIOMER; NUCLEAR MAGNETIC RESONANCE; PRIORITY JOURNAL; REACTION ANALYSIS;

EID: 0030272830     PISSN: 09574166     EISSN: None     Source Type: Journal    
DOI: 10.1016/0957-4166(96)00359-X     Document Type: Article

References (37)

1. 1. For reviews, see: (a) Sapi, J.; Massiot, G. In Monoterpenoid Indole Alkaloids, Saxton, J. E., Ed. In The Chemistry of Heterocyclic Compounds, Taylor, E. C., Ed. Supplement to Vol. 25, Part 4, pp. 279-355, Wiley: New York, 1994.
2. (b) Bosch, J.; Bonjoch, J.; Amat, M. In The Alkaloids, Cordell, G. A., Ed. Vol. 48, pp 75-189, Academic Press: New York, 1996.
3. For more recent total syntheses, see: (c) Bonjoch, J.; Solé, D.; Bosch, J. J. Am. Chem. Soc. 1995, 117, 11017.
4. (d) Solé, D.; Bonjoch, J.; Bosch, J. J. Org. Chem. 1996, 61, 4194.
5. (e) Solé, D.; Bonjoch, J.; Garciá-Rubio, S.; Suriol, R.; Bosch, J. Tetrahedron Lett. 1996, 37, 5213.
6. 2. Knight, S. D.; Overman, L. E.; Pairaudeau, G. J. Am. Chem. Soc. 1995, 117, 5776.
7. 3. The synthesis of (-)-tubifolidine following the methodology reported in reference 1e has recently been completed in our laboratory.
8. 4. (a) 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.
9. (b) Amat, M.; Coll, M.-D.; Bosch, J. Tetrahedron 1995, 51, 10759.
10. 5. Micouin, L.; Diez, A.; Castells, J.; López, D.; Rubiralta, M.; Quirion, J.-C.; Husson, H.-P. Tetrahedron Lett. 1995, 36, 1693.
11. 6. (a) For the isolation and structural elucidation of this alkaloid, see: Kump, W. G.; Patel, M. B.; Rowson, J. M.; Schmid, H. Helv. Chim. Acta 1964,47, 1497.
12. Before its isolation, (-)-tubifoline was a known compound which had been obtained by partial synthesis in the context of the structural elucidation of more complex Strychnos alkaloids: (b) Bernauer, K.; Arnold, W.; Weissmann, Ch.; Schmid, H.; Karrer, P. Helv. Chim. Acta 1960, 43, 717.
13. (c) Schumann, D.; Schmid, H. Helv. Chim. Acta 1963, 46, 1996.
14. (d) Weissmann, Ch.; Schmid, H.; Karrer, P. Helv. Chim. Acta 1961, 44, 1877.
15. 7. The biogenetic numbering and ring labeling is used: Le Men, J; Taylor, W. I. Experientia 1965, 21, 508.
16. 3)].
17. 9. For the preparation of optically pure 1-(pyridyl)ethanols by lipase-catalyzed transesterification, see: (a) Seemayer, R.; Schneider, M. P. Tetrahedron: Asymmetry 1992, 3, 827.
18. (b) Orrenius, C.; Mattson, A.; Norin, T.; Öhrner, N.; Hult, K. Tetrahedron: Asymmetry 1994, 5, 1363.
19. 10. The inversion of the unreacted S alcohol (-)-2 to the R enantiomer has been reported: see reference 11.
20. 11. Uskokovic, M. R.; Lewis, R. L.; Partridge, J. J.; Despreaux, C. W.; Pruess, D. L. J. Am. Chem. Soc. 1979, 101, 6742.
21. 2).
22. 13. Smith, A. B.; Visnick, M.; Haseltine, J. N.; Sprengeler, P. A. Tetrahedron 1986,42, 2957.
23. 14. (a) For a related photocyclization, see: Wu, A.; Snieckus, V. Tetrahedron Lett. 1975, 2057.
24. (b) For a review, see: Sundberg, R. J. Organic Photochemistry, Padwa, A., Ed. Vol. 6, pp 121-176, Marcel Dekker: New York, 1983.
25. 3, 75 MHz) δ 12.4 (C-18), 29.7 (C-14), 31.3 (C-16), 33.3 (C-6), 38.2 (C-3), 38.4 (C-15), 49.1 (C-21), 104.8 (C-7), 110.3 (C-12), 117.4 (C-9), 119.0 (C-10), 118.5 (C-19), 121.3 (C-11), 127.8 (C-8), 133.9 (C-13), 134.7 (C-2), 136.4 (C-20), 173.3 (C-5).
26. 16. From the synthetic standpoint it was more convenient to use the mixture of Z/E lactams and then to hydrogenate the resulting Z/E mixture of unsaturated tetracyclic amines.
27. 3, 75 MHz) δ 12.5 (C-18), 24.6 (C-6), 26.7 (C-14), 36.7 (C-16), 36.8 (C-15), 44.8 (C-3), 47.7 (C-21), 57.6 (C-5), 110.4 (C-12), 110.8 (C-7), 117.6 (C-9), 118.6 (C-19), 118.7 (C-10), 120.6 (C-11), 128.2 (C-8), 135.0 (C-13), 135.2 (C-2), 142.7 (C-20).
28. 3, 75 MHz) δ 12.0 (C-18), 24.1 (C-19), 24.8 (C-6), 28.0 (C-14), 30.3 (C-20), 30.4 (C-16), 38.5 (C-15), 45.2 (C-3), 48.5 (C-21), 55.9 (C-5), 110.3 (C-12), 110.7 (C-7), 117.4 (C-9), 118.7 (C-10), 120.5 (C-11), 128.5 (C-8), 134.8 (C-2), 136.1 (C-13).
29. 19. (a) Amine 12 is a known product, first prepared by degradation of akuammicine: Smith, G. T.; Wróbel, J. T. J. Chem. Soc. 1960, 792.
30. For syntheses of rac-12, see: (b) Dadson, B. A.; Harley-Mason, J.; Foster, G. H. Chem. Commun. 1968, 1233.
31. (c) Ban, Y.; Yoshida, K.; Goto, J.; Oishi, T.; Takeda, E. Tetrahedron 1983, 39, 3657.
32. (d) See also reference 14a.
33. -1, 254 nm) and racemic tubifoline as reference.
34. 21) was also isolated as a minor product in some runs.
35. 22. For a similar "spontaneous" transannular oxidative cyclization in a tetracyclic stemmadenine-type system, see reference 4a.
36. 23. (a) For previous syntheses of racemic tubifoline by oxidative transannular cyclization of rac-12, see references 19b,c.
37. (b) For a different total synthesis of racemic tubifoline, see: Amat, M.; Linares, A.; Bosch, J. J. Org. Chem. 1990, 55, 6299.