1. Enantioselective Total Synthesis of (+)-Gelsemine
YOKOSHIMA, s.; Tokuyama, H.; Fukuyama, T. Angew. Chem. Int. Ed. 2000, 39,
A presentation BY Guillaume Pelletier

2. (+)-Gelsemine Isolated from gelsemium sempervirens.
Its structure was determined in 1959 by Conroy
and Chakrabarti by degrative and
spectroscopic data.
Crystallographic determination by Lovell et al.
No (or sketchy) biological activity.
7 total syntheis of Gelsemine up to date.
Lin, H.; Danishefsky, S. J. Angew. Chem. Int. Ed. 2003, 42,

3. Racemic Gelsemine Synthesis
3 Racemic total synthesis before the synthesis of Fukuyama:
Lin, H.; Danishefsky, S. J. Angew. Chem. Int. Ed. 2003, 42,

4. Retrosynthetic analysis by Fukuyama
Yokoshima, S.; Tokuyama, H.; Fukuyama, T. Angew. Chem. Int. Ed. 2000, 39,

5. Steps 1-3
Yokoshima, S.; Tokuyama, H.; Fukuyama, T. Angew. Chem. Int. Ed. 2000, 39,

6. Diels-Alder with Evans’ oxazolidinone
Evans, D. A.; Chapman, K. T.; Bisaha, J. J. Am. Chem. Soc. 1988, 110,

7. Steps 1-3
Yokoshima, S.; Tokuyama, H.; Fukuyama, T. Angew. Chem. Int. Ed. 2000, 39,

8. Steps 1-3
Yokoshima, S.; Tokuyama, H.; Fukuyama, T. Angew. Chem. Int. Ed. 2000, 39,

9. Tamao-Fleming oxidation
Jones, G. R.; Landais, Y. Tetrahedron 1996, 52,

10. Steps 4-7
Yokoshima, S.; Tokuyama, H.; Fukuyama, T. Angew. Chem. Int. Ed. 2000, 39,

11. Lewis acid – catalyzed cationic fragmentation
Maruoka, K.; Itoh, T.; Sakurai, M.; Nonoshita, K.; Yamamoto, H. J. Am. Chem. Soc. 1988, 110,

12. Synthesis of 4-iodooxindole
Fukuyama, T.; Liu, G. J. Am. Chem. Soc. 1996, 118,

13. Steps 4-7
Yokoshima, S.; Tokuyama, H.; Fukuyama, T. Angew. Chem. Int. Ed. 2000, 39,

14. Condensation with oxoindole

15. Steps 4-7
Yokoshima, S.; Tokuyama, H.; Fukuyama, T. Angew. Chem. Int. Ed. 2000, 39,

16. Steps 8-13
Yokoshima, S.; Tokuyama, H.; Fukuyama, T. Angew. Chem. Int. Ed. 2000, 39,

17. Divinylcyclopropane rearrangement (Cope)

18. Steps 8-13
Yokoshima, S.; Tokuyama, H.; Fukuyama, T. Angew. Chem. Int. Ed. 2000, 39,

19. Horner-Wadsworth Emmonds
Minami, T.; Okauchi, T.; Kouno, R. Synthesis 2001,

20. Steps 8-13
Yokoshima, S.; Tokuyama, H.; Fukuyama, T. Angew. Chem. Int. Ed. 2000, 39,

21. Radical dehalogenation

22. Steps 14 to 20
Yokoshima, S.; Tokuyama, H.; Fukuyama, T. Angew. Chem. Int. Ed. 2000, 39,

23. Steps 21 to 25
Yokoshima, S.; Tokuyama, H.; Fukuyama, T. Angew. Chem. Int. Ed. 2000, 39,

24. Grieco’s procedure – Seleno-dehydradtion
Grieco, P. A.; Gilman. S.; Nishizawa, M. J. Org. Chem. 1976, 41, 1485.

25. Steps 21 to 25
Yokoshima, S.; Tokuyama, H.; Fukuyama, T. Angew. Chem. Int. Ed. 2000, 39,

26. Polonovski Reaction
Sundberg, R. J.; Gadamasetti, K. G.; Hunt, P. J. Tetrahedron 1992, 48,

27. Polonovski Reaction
Sundberg, R. J.; Gadamasetti, K. G.; Hunt, P. J. Tetrahedron 1992, 48,

28. Polonovski – like elimination
Yokoshima, T.; Kubo, T.; Tokuyama, H.; Fukuyama, T. Chem. Lett. 2002,

29. Steps 26 to (+)-Gelsemine
Yokoshima, S.; Tokuyama, H.; Fukuyama, T. Angew. Chem. Int. Ed. 2000, 39,