Stereocontrolled total synthesis of (±)-gelsemine

Journal of the American Chemical Society

Volumn 118, Issue 31, 1996, Pages 7426-7427

  Fukuyama, Tohru ^b   Liu, Gang ^a,c  

^a RICE UNIVERSITY   (United States)

^b UNIVERSITY OF TOKYO   (Japan)

^c ABBOTT LABORATORIES   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKALOID; GELSEMINE; UNCLASSIFIED DRUG;

ARTICLE; DRUG SYNTHESIS; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0029759532     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja961701s     Document Type: Article

References (25)

1. For reviews of Gelsemium alkaloids, see: (a) Liu, Z,-J.; Lu, R.-R. In The Alkaloids; Manske, R. H. F., Ed.; Academic Press: New York, 1988; Vol. 33, pp 83-140.
2. (b) Saxton, J. E. In The Alkaloids: Manske, R. H. F., Ed.; Academic Press: New York, 1965; Vol. 8. pp 93-117.
3. (a) Lovell, F. M.; Pepinsky, R.; Wilson, A. J. C. Tetrahedron Lett. 1959, No. 4, 1-5.
4. (b) Conroy, H.; Chakrabarti, J. K. Tetrahedron Lett. 1959, No. 4, 6-13.
5. (a) Fleming, I.; Moses, R. C.; Tercel, M.; Ziv, J. J. Chem. Soc., Perkin Trans. 1 1991, 617-626.
6. (b) Stork, G.; Nakatani, K. Tetrahedron Lett. 1988, 29, 2283-2286.
7. (c) Madin, A.; Overman, L. E. Tetrahedron Lett. 1992, 33, 4859-4862.
8. (a) Dutton, J. K.; Steel, R. W.; Tasker, A. S.; Popsavin, V.; Johnson, A. P. J. Chem. Soc., Chem. Commun. 1994, 765-766.
9. (b) Newcomb, N. J.; Ya, F.; Vijn, R. J.; Hiemstra, H.; Speckamp, W. N. J. Chem. Soc., Chem. Commun. 1994, 767-768.
10. (c) Kuzmich, D.; Wu, S. C.; Ha. D.-C.; Lee, C-S.; Ramesh, S.; Atarashi, S.; Choi, J.-K.; Hart, D. J. J. Am. Chem. Soc. 1994, 116, 6943-6944.
11. For a review of this interesting rearrangement, see: Hudlicky, T.; Fan, R.; Reed, J. W.; Gadamasetti, K. G. Org. React. 1992, 41, 1-133.
12. Kondo, K.; Umemoto, T.; Yako, K.; Tunemoto, D. Tetrahedron Lett. 1978, 19, 3927-3930.
13. According to the PM3 calculation, the iodinated Z-isomer is more stable than the E-isomer by 9.4 kcal/mol (MOPAC Version 94.1 in CAChe, Version 3.6, CAChe Scientific, 1994).
14. 2, then KI, 0-90 °C;
15. 4 70 °C;
16. 2O, 23 °C;
17. 4, 110 °C;
18. 2O (3:1), 23 °C].
19. Pfitzner, K. E.; Moffatt, J. G. J. Am. Chem. Soc. 1965, 87, 5661-5670.
20. Compound 10 gradually rearranged to 11a when stored at room temperature.
21. Brown, H. C.; Narasimhan, S. J. Org. Chem. 1982, 47, 1604-1606.
22. Deziel, R. Tetrahedron Lett. 1987, 28, 4371-4372.
23. Tebbe, F. N.; Parshall, G. W.; Reddy, G. S. J. Am. Soc. Chem. 1978, 100, 3611-3613.
24. Benhamou, M. C.; Etemad-Moghadam, G.; Speziale, V.; Lattes, A. Synthesis 1979, 891-893. We thank Professor W. Nico Speckamp of the University of Amsterdam for informing us that a high concentration of the substrate (0.4 M) is essential for the reductive demercuration.
25. We are indebted to Professor Geoffrey A. Cordell of the University of Illinois at Chicago for the authentic samples of both 21-oxogelsemine and gelsemine.