Stereocontrolled total synthesis of (±)-gelsemine

Pure and Applied Chemistry

Volumn 69, Issue 3, 1997, Pages 501-505

  Fukuyama, Tohru ^a   Liu, Gang ^b  

^a UNIVERSITY OF TOKYO   (Japan)

^b RICE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000699370     PISSN: 00334545     EISSN: None     Source Type: Journal    
DOI: 10.1351/pac199769030501     Document Type: Article

References (21)

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. 2O (3:1), 23°C].
15. Pfitzner, K. E.; Moffatt, J. G. J. Am. Chem. Soc. 1965, 87, 5661-5670.
16. Compound 18 gradually rearranged to 19a when stored at room temperature.
17. Brown, H. C.; Narasimhan, S. J. Org. Chem. 1982, 47, 1604-1606.
18. Deziel, R. Tetrahedron Lett. 1987, 28, 4371-4372.
19. Tebbe, F. N.; Parshall, G. W.; Reddy, G. S. J. Am. Soc. Chem. 1978, 100, 3611-3613.
20. 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 the fact that high concentration of the substrate (0.4 M) is essential for the reductive demercuration.
21. 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.