Nonlinear effects in the reduction of acetophenone by diisopinocampheyl chloroborane: Influence of the stoichiometry of the reagent

Tetrahedron Asymmetry

Volumn 8, Issue 23, 1997, Pages 3851-3854

  Girard, Christian ^a   Kagan, Henri B ^a  

^a CNRS   (France)

Author keywords

[No Author keywords available]

Indexed keywords

1 PHENYLETHANOL; ACETOPHENONE; BORANE DERIVATIVE; DIISOPINOCAMPHEYL CHLOROBORANE; REAGENT; UNCLASSIFIED DRUG;

ARTICLE; PRIORITY JOURNAL; REDUCTION; STOICHIOMETRY;

EID: 0031468991     PISSN: 09574166     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0957-4166(97)00592-2     Document Type: Article

References (20)

1. Brown, H. C.; Zweifel, G. J. Am. Chem. Soc. 1961, 83, 486. Zweifel, G.; Brown, H. C. J. Am. Chem. Soc. 1964, 86, 393. Brown, H. C.; Ayyangar; N. R.; Zweifel, G. J. Am. Chem. Soc. 1964, 86, 397. Brown, H. C.; Joshi, N. N. J. Org. Chem. 1988, 53, 4059.
2. Brown, H. C.; Zweifel, G. J. Am. Chem. Soc. 1961, 83, 486. Zweifel, G.; Brown, H. C. J. Am. Chem. Soc. 1964, 86, 393. Brown, H. C.; Ayyangar; N. R.; Zweifel, G. J. Am. Chem. Soc. 1964, 86, 397. Brown, H. C.; Joshi, N. N. J. Org. Chem. 1988, 53, 4059.
3. Brown, H. C.; Zweifel, G. J. Am. Chem. Soc. 1961, 83, 486. Zweifel, G.; Brown, H. C. J. Am. Chem. Soc. 1964, 86, 393. Brown, H. C.; Ayyangar; N. R.; Zweifel, G. J. Am. Chem. Soc. 1964, 86, 397. Brown, H. C.; Joshi, N. N. J. Org. Chem. 1988, 53, 4059.
4. Brown, H. C.; Zweifel, G. J. Am. Chem. Soc. 1961, 83, 486. Zweifel, G.; Brown, H. C. J. Am. Chem. Soc. 1964, 86, 393. Brown, H. C.; Ayyangar; N. R.; Zweifel, G. J. Am. Chem. Soc. 1964, 86, 397. Brown, H. C.; Joshi, N. N. J. Org. Chem. 1988, 53, 4059.
5. Brown, H. C.; Singaram, B. Acc. Chem. Res. 1988, 21, 287.
6. Brown, H. C.; Desai, M. C.; Jadhav, P. K. J. Org. Chem. 1982, 47, 4059. Brown, H. C.; Jadhav, P. K.; Mandal, A. K. J. Org. Chem. 1982, 47, 5074. Brown, H. C.; Vara Prasad, J. V. N. J. Am. Chem. Soc. 1986, 108, 2049.
7. Brown, H. C.; Desai, M. C.; Jadhav, P. K. J. Org. Chem. 1982, 47, 4059. Brown, H. C.; Jadhav, P. K.; Mandal, A. K. J. Org. Chem. 1982, 47, 5074. Brown, H. C.; Vara Prasad, J. V. N. J. Am. Chem. Soc. 1986, 108, 2049.
8. Brown, H. C.; Desai, M. C.; Jadhav, P. K. J. Org. Chem. 1982, 47, 4059. Brown, H. C.; Jadhav, P. K.; Mandal, A. K. J. Org. Chem. 1982, 47, 5074. Brown, H. C.; Vara Prasad, J. V. N. J. Am. Chem. Soc. 1986, 108, 2049.
9. Chandrasekharan, J.; Ramachandran, P. V.; Brown, H. C. J. Org. Chem. 1985, 50, 5448.
10. Puchot, C.; Samuel, O.; Duñach, E.; Zhao, S.; Agami, C.; Kagan, H. B. J. Am. Chem. Soc. 1986, 108, 2353. Guillaneux, D.; Zhao, S. H.; Samuel, O.; Rainford, D.; Kagan, H. B. J. Am. Chem. Soc. 1994, 116, 9430. Zhang, S. Y.; Girard, C.; Kagan, H. B. Tetrahedron: Asymmetry 1995, 6, 2637. Kagan, H. B.; Girard, C.; Guillaneux, D.; Rainford, D.; Samuel, O.; Zhang, S. Y.; Zhao, S. H. Acta Chim. Scand. 1995, 50, 345.
11. Puchot, C.; Samuel, O.; Duñach, E.; Zhao, S.; Agami, C.; Kagan, H. B. J. Am. Chem. Soc. 1986, 108, 2353. Guillaneux, D.; Zhao, S. H.; Samuel, O.; Rainford, D.; Kagan, H. B. J. Am. Chem. Soc. 1994, 116, 9430. Zhang, S. Y.; Girard, C.; Kagan, H. B. Tetrahedron: Asymmetry 1995, 6, 2637. Kagan, H. B.; Girard, C.; Guillaneux, D.; Rainford, D.; Samuel, O.; Zhang, S. Y.; Zhao, S. H. Acta Chim. Scand. 1995, 50, 345.
12. Puchot, C.; Samuel, O.; Duñach, E.; Zhao, S.; Agami, C.; Kagan, H. B. J. Am. Chem. Soc. 1986, 108, 2353. Guillaneux, D.; Zhao, S. H.; Samuel, O.; Rainford, D.; Kagan, H. B. J. Am. Chem. Soc. 1994, 116, 9430. Zhang, S. Y.; Girard, C.; Kagan, H. B. Tetrahedron: Asymmetry 1995, 6, 2637. Kagan, H. B.; Girard, C.; Guillaneux, D.; Rainford, D.; Samuel, O.; Zhang, S. Y.; Zhao, S. H. Acta Chim. Scand. 1995, 50, 345.
13. Puchot, C.; Samuel, O.; Duñach, E.; Zhao, S.; Agami, C.; Kagan, H. B. J. Am. Chem. Soc. 1986, 108, 2353. Guillaneux, D.; Zhao, S. H.; Samuel, O.; Rainford, D.; Kagan, H. B. J. Am. Chem. Soc. 1994, 116, 9430. Zhang, S. Y.; Girard, C.; Kagan, H. B. Tetrahedron: Asymmetry 1995, 6, 2637. Kagan, H. B.; Girard, C.; Guillaneux, D.; Rainford, D.; Samuel, O.; Zhang, S. Y.; Zhao, S. H. Acta Chim. Scand. 1995, 50, 345.
14. Girard, C.; Kagan, H. B. Tetrahedron: Asymmetry 1995, 6, 1881.
15. King, A. O.; Corley, E. G.; Anderson, R. K.; Larsen, R. D.; Verhoeven, T. R.; Reider, P. J.; Xiang, Y. B.; Belley, M.; Leblanc, Y.; Labelle, M.; Prasit, P.; Zamboni, R. J. J. Org. Chem. 1993, 58, 3731. Shinkai, I.; King, A. O.; Larsen, R. D. Pure & Appl. Chem. 1994, 66, 1551.
16. King, A. O.; Corley, E. G.; Anderson, R. K.; Larsen, R. D.; Verhoeven, T. R.; Reider, P. J.; Xiang, Y. B.; Belley, M.; Leblanc, Y.; Labelle, M.; Prasit, P.; Zamboni, R. J. J. Org. Chem. 1993, 58, 3731. Shinkai, I.; King, A. O.; Larsen, R. D. Pure & Appl. Chem. 1994, 66, 1551.
17. t=11 min.
18. In general, the yields of the reductions follow this rule. However, inacuraccies of measurement of some conversions prevent curves being drawn.
19. Zhao, M.; King, A. O.; Larsen, R. D.; Verhoeven, T. R.; Reider, P. J. Tetrahedron Lett. 1997, 38, 2641.
20. If one assumes the statistical formation of the three boron reagents and complete inactivity of the meso reagent, the ee of (R)-4 must be independent of the amount of reagent and is easily calculated. It gives the statistical curve depicted in Scheme 2. This curve is very different from the experimental ones. This is additional confirmation of the complexity of the system.