Mathematical models of nonlinear effects in asymmetric catalysis: New insights based on the role of reaction rate

Journal of the American Chemical Society

Volumn 119, Issue 52, 1997, Pages 12934-12939

  Blackmond, Donna G ^a  

^a MAX PLANCK INSTITUT FÜR KOHLENFORSCHUNG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ARTICLE; CATALYSIS; CHIRALITY; COUPLING FACTOR; ENANTIOMER; MATHEMATICAL MODEL; NONHUMAN; PROTEIN STRUCTURE; REACTION ANALYSIS;

EID: 0031593113     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja973049m     Document Type: Article

References (22)

1. (a) Guillaneux, D.; Zhao, S. H.; Samuel, O.; Rainford, D.; Kagan, H. B. J. Am. Chem. Soc. 1994, 116, 9430-39.
2. (b) Puchot, C.; Samuel, O.; Duñach, E.; Zhao, S.; Agami, C.; Kagan, H. B. J. Am. Chem. Soc. 1986, 108, 2353-57.
3. (c) Oguni, N.; Matsuda, Y.; Kaneko, T. J. Am. Chem. Soc. 1988, 110, 7877.
4. (d) Noyori, R.; Kitamura, M. Angew. Chem., Int. Ed. Engl. 1991, 30, 49-69.
5. (e) Kitamura, M.; Suga, S.; Niwa, M.; Noyori, R. J. Am. Chem. Soc. 1995, 117, 4832-4842.
6. (f) Bolm, C. Tetrahedron: Asymmetry 1991, 2, 701-704.
7. (g) Mikami, K.; Motoyama, Y.; Terada, M. J. Am. Chem. Soc. 1988, 116, 2812-2820.
8. (h) Mikami, K.; Matsukawa T. Tetrahedron 1992, 48, 5671-80.
9. (i) Keck, G. E.; Krishnamurthy, D.; Grier, M. C. J. Org. Chem. 1993, 58, 6543-6544.
10. See also these reviews: (a) Kagan, J. B.; Girard, C.; Guillaneux, D.; Rainford, D.; Samuel, O.; Zhand, S. Y.; Zhao, S. H. Acta Chem. Scand. 1996, 30, 345-352. (b) Bolm, C. In Advanced Asymmetric Synthesis; Stephenson, G. R., Ed.; Blackie A&P: Glasgow, 1996; pp 9-26.
11. See also these reviews: (a) Kagan, J. B.; Girard, C.; Guillaneux, D.; Rainford, D.; Samuel, O.; Zhand, S. Y.; Zhao, S. H. Acta Chem. Scand. 1996, 30, 345-352. (b) Bolm, C. In Advanced Asymmetric Synthesis; Stephenson, G. R., Ed.; Blackie A&P: Glasgow, 1996; pp 9-26.
12. Figure 1a in this paper reproduces the model fit given in Figure 5a of ref 1a.
13. x models.
14. For reports on chiral poisoning, see: (a) Alcock, N. W.; Brown, J. M.; Maddox, P. J. J. Chem. Soc., Chem. Commun. 1986, 1532-33. (b) Maraoka, K.; Yamamoto, H. J. Am. Chem. Soc. 1989, 115, 789-90. (c) Faller, J. W.; Parr, J. J. Äm. Chem. Soc. 1993, 115, 804-05. Kagan and co-workers have also pointed out how the concept of chiral poisoning increases the concentration of enantiopure catalyst within the catalytic cycle.
15. For reports on chiral poisoning, see: (a) Alcock, N. W.; Brown, J. M.; Maddox, P. J. J. Chem. Soc., Chem. Commun. 1986, 1532-33. (b) Maraoka, K.; Yamamoto, H. J. Am. Chem. Soc. 1989, 115, 789-90. (c) Faller, J. W.; Parr, J. J. Äm. Chem. Soc. 1993, 115, 804-05. Kagan and co-workers have also pointed out how the concept of chiral poisoning increases the concentration of enantiopure catalyst within the catalytic cycle.
16. For reports on chiral poisoning, see: (a) Alcock, N. W.; Brown, J. M.; Maddox, P. J. J. Chem. Soc., Chem. Commun. 1986, 1532-33. (b) Maraoka, K.; Yamamoto, H. J. Am. Chem. Soc. 1989, 115, 789-90. (c) Faller, J. W.; Parr, J. J. Äm. Chem. Soc. 1993, 115, 804-05. Kagan and co-workers have also pointed out how the concept of chiral poisoning increases the concentration of enantiopure catalyst within the catalytic cycle.
17. (a) Jacobsen, E. N.; Marko, I.; France, M. B.; Svendsen, J. S.; Sharpless, K. B. J. Am. Chem. Soc. 1989, 111, 737-739.
18. (b) Berrisford, D. J.; Bolm, C.; Sharpless, K. B. Angew. Chem. 1995, 34, 1059-1070.
19. A related idea described recently is called "chiral activation". Addition of a species which selectively interacts with one enantiomer in a racemic catalyst mixture resulted in a significant rate acceleration of the reaction carried out by the activated catalyst species. No "sacrifice" of either catalytic species occurs in this case; in fact, the remaining, unactivated enantiomer continues to react with its intrinsic activity and (opposite) enantioselectivity: (a) Mikami, K.; Matsukawa T. Nature 1997, 385, 613-15. (b) Matsukawa, T.; Mikami, K. Tetrahedron: Asymmetry 1997, 8, 815-816.
20. A related idea described recently is called "chiral activation". Addition of a species which selectively interacts with one enantiomer in a racemic catalyst mixture resulted in a significant rate acceleration of the reaction carried out by the activated catalyst species. No "sacrifice" of either catalytic species occurs in this case; in fact, the remaining, unactivated enantiomer continues to react with its intrinsic activity and (opposite) enantioselectivity: (a) Mikami, K.; Matsukawa T. Nature 1997, 385, 613-15. (b) Matsukawa, T.; Mikami, K. Tetrahedron: Asymmetry 1997, 8, 815-816.
21. R would most likely be further differentiated by their relative positions in the coordination sphere of the metal: for example, in an octahedral complex, the intrinsic enantioselectivities of catalysts containing homochiral ligands cis to one another could be different than that of a complex where heterochiral ligands are in a cis configuration.
22. Details on these calculations are available in the Supporting Information.