Nonlinear effects as 'indicators' in the tuning of asymmetric catalysts

Tetrahedron Asymmetry

Volumn 9, Issue 11, 1998, Pages 1941-1946

  Brunel, Jean Michel ^a   Luukas, Timo O ^a   Kagan, Henri B ^a  

^a UNIVERSITÉ PARIS SUD   (France)

Author keywords

[No Author keywords available]

Indexed keywords

TITANIUM DERIVATIVE;

ARTICLE; CATALYST; CHEMICAL REACTION; CHIRALITY; ENANTIOMER; OXIDATION; PRIORITY JOURNAL; STOICHIOMETRY; SYNTHESIS;

EID: 0032486159     PISSN: 09574166     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0957-4166(98)00168-2     Document Type: Article

References (26)

1. 1. For recent reviews on NLE see Ref. 2. Initial reports on NLE between 1986 and 1990: Refs. 3-6. Simplified models for discussing NLE: Refs. 7 and 8.
2. 2. (a) Kagan, H. B.; Girard, C.; Guillaneux, D.; Rainford, D.; Samuel, O.; Zhang, S. Y.; Zhao, S. H. Acta Chem. Scand., 1996, 50, 345; Avalos, M.; Babiano, R.; Cintas, P.; Jiménez, J. L.; Palacios, J. C. Tetrahedron: Asymmetry, 1997, 8, 2997;
3. 2. (a) Kagan, H. B.; Girard, C.; Guillaneux, D.; Rainford, D.; Samuel, O.; Zhang, S. Y.; Zhao, S. H. Acta Chem. Scand., 1996, 50, 345; Avalos, M.; Babiano, R.; Cintas, P.; Jiménez, J. L.; Palacios, J. C. Tetrahedron: Asymmetry, 1997, 8, 2997;
4. (c) Bolm, C. In Advanced Asymmetric Catalysis, Ed. Stephenson, G. R., Blackie Academic and Professional, New York, 1996, pp. 9-26.
5. 3. Puchot, C.; Samuel, O.; Dunach, E.; Zhao, S.; Agami, C.; Kagan, H. B. J. Am. Chem. Soc., 1986, 108, 2353.
6. 4. Oguni, N.; Matsuda, Y.; Kaneko, T. J. Am. Chem. Soc., 1988, 110, 7877.
7. 5. Kitamura, M.; Okada, S.; Suga, S.; Noyori, R. J. Am. Chem. Soc., 1989, 111, 4028.
8. 6. Terada, M.; Mikami, K.; Nakai, T. J. Chem. Soc., Chem. Commun., 1990, 1623.
9. 7. Guillaneux, D.; Zhao, S. H.; Rainford, D.; Samuel, O.; Kagan, H. B. J. Am. Chem. Soc., 1994, 116, 9430.
10. 8. Blackmond, D. G. J. Am. Chem. Soc., 1997, 119, 12934.
11. 9. Kitamura, M.; Suga, S.; Niwa, M.; Noyori, R. J. Am. Chem. Soc., 1995, 117, 4832.
12. 10. Zondervan, C.; Feringa, B. L. Tetrahedron: Asymmetry, 1996, 7, 1895.
13. 11. Kobayashi, S.; Ishitani, H.; Araki, M.; Hachiya, I. Tetrahedron Lett., 1994, 35, 6325.
14. 12. Pitchen, P.; Dunach, E.; Deshmukh, M. N.; Kagan, H. B. J. Am. Chem. Soc., 1984, 106, 8188.
15. 13. Di Furia, F.; Modena, G.; Seraglia, R. Synthesis, 1984, 325.
16. 14. Brunel, J. M.; Diter, P.; Duetsch, M.; Kagan, H. B. J. Org. Chem., 1995, 60, 8036.
17. 15. Brunel, J. M.; Kagan, H. B. Synlett, 1996, 404.
18. 16. Brunel, J. M.; Kagan, H. B. Bull. Soc. Chim. Fr., 1996, 133, 1109.
19. 4 and tartrates in several relative amounts see, Berrisford, D. J.; Bolm, C.; Sharpless, K. B. Angew. Chem. Int. Ed. Engl., 1995, 34, 1059.
20. 18. Diter, P.; Taudien, S.; Samuel, O.; Kagan, H. B. J. Org. Chem., 1994, 59, 370.
21. 19. For a prediction of multi-shape NLE curves based on a simple kinetic model see Ref. 7. For a case of the NLE curve crossing the straight line see, Tanaka, K.; Mitsui, J.; Kawabata, H.; Watanabe, A. J. Chem. Soc., Chem. Comm., 1991, 1632.
22. 20. Sulfoxide 2 has 81% ee at 50% conversion and 90% ee at 90% conversion. A simple calculation indicates that the catalyst must produce essentially enantiomerically pure sulfoxide beyond 50% conversion.
23. 21. Asymmetric autoinduction (modification of the catalyst by the product) may be operating here (see, Alberts, A. H.; Wynberg, H. J. Am. Chem. Soc., 1989, 111, 7265; Bolm, C.; Bienewald, H.; Seger, A. Angew. Chem. Int. Ed. Engl., 1996, 35, 1657). However, addition of either enantiomer of 2 at the beginning of the reaction did not improve the enantio selectivity.
24. 21. Asymmetric autoinduction (modification of the catalyst by the product) may be operating here (see, Alberts, A. H.; Wynberg, H. J. Am. Chem. Soc., 1989, 111, 7265; Bolm, C.; Bienewald, H.; Seger, A. Angew. Chem. Int. Ed. Engl., 1996, 35, 1657). However, addition of either enantiomer of 2 at the beginning of the reaction did not improve the enantio selectivity.
25. 4 has been found to be devoid of catalytic activity in sulfoxidation and cannot be responsible for a (-)-NLE.
26. 4/DET. In both cases an inversion of the sign of NLE with catalytic amount has been observed, as in sulfoxidation (unpublished results).