Transition-state model for subtilisin-catalyzed transesterifications of secondary alcohols

Tetrahedron Letters

Volumn 40, Issue 23, 1999, Pages 4367-4370

  Tadashi, Ema ^a   Okada, Ryoichi ^a   Fukumoto, Minoru ^a   Jittani, Masahito ^a   Ishida, Mikiko ^a   Furuie, Kenji ^a   Yamaguchi, Kunihiro ^a   Sakai, Takashi ^a   Utaka, Masanori ^a  

^a OKAYAMA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL DERIVATIVE; SUBTILISIN;

ACYLATION; ARTICLE; CATALYSIS; CHEMICAL REACTION KINETICS; CHEMICAL STRUCTURE; CRYSTAL STRUCTURE; ENANTIOMER; ESTERIFICATION; STEREOCHEMISTRY; SYNTHESIS;

EID: 0033523059     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)00750-9     Document Type: Article

References (16)

1. (a) Lee, T.; Jones, J. B. J. Am. Chem. Soc. 1996, 118, 502-508.
2. (b) Ke, T.; Wescott, C. R.; Klibanov, A. M. J. Am. Chem. Soc. 1996, 118, 3366-3374.
3. (a) Kazlauskas, R. J.; Weissfloch, A. N. E.; Rappaport, A. T.; Cuccia, L. A. J. Org. Chem. 1991, 56, 2656-2665.
4. (b) Cygler, M.; Grochulski, P.; Kazlauskas, R. J.; Schrag, J. D.; Bouthillier, F.; Rubin, B.; Serreqi, A. N.; Gupta, A. K. J. Am. Chem. Soc. 1994, 116, 3180-3186.
5. (c) Nakamura, K.; Kawasaki, M.; Ohno, A. Bull. Chem. Soc. Jpn. 1996, 69, 1079-1085.
6. Ema, T.; Kobayashi, J.; Maeno, S.; Sakai, T.; Utaka, M. Bull. Chem. Soc. Jpn. 1998, 71, 443-453.
7. Ema, T.; Jittani, M.; Sakai, T.; Utaka, M. Tetrahedron Lett. 1998, 39, 6311-6314.
8. Wang, Y.-F.; Yakovlevsky, K.; Zhang, B.; Margolin, A. L. J. Org. Chem. 1997, 62, 3488-3495. ChiroCLEC-BL (dry powder) purchased from Altus Biologies Inc. (USA) was used.
9. Chen, C.-S.; Fujimoto, Y.; Girdaukas, G.; Sih, C. J. J. Am. Chem. Soc. 1982, 104, 7294-7299.
10. The S-preference of subtilisins for secondary alcohols has also been reported elsewhere. (a) Fitzpatrick, P. A; Klibanov, A. M. J. Am. Chem. Soc. 1991, 113, 3166-3171.
11. (b) Kazlauskas, R. J.; Weissfloch, A. N. E. J. Mol. Cat. B: Enz. 1997, 3, 65-72.
12. (c) Lloyd, R. C.; Dickman, M.; Jones, J. B. Tetrahedron: Asymmetry 1998, 9, 551-561. See also ref 5.
13. Alcohols 6 and 7 are the exceptions. This is probably because even the (S)-enantiomers of 6 and 7 undergo steric hindrance, judging from the low reactivity and the low E values of 6 and 7.
14. For example: McPhalen, C. A; James, M. N. G. Biochemistry 1988, 27, 6582-6598.
15. Derewenda, Z. S.; Wei, Y. J. Am. Chem. Soc. 1995, 117, 2104-2105.
16. The enantioselectivity in the lipase-catalyzed kinetic resolutions of 8 was complete, because the slower-reacting (S)-enantiomer of 8 did not undergo the acylation at all.