Theoretical Studies on Asymmetric Boron-catalyzed Reaction(Ⅰ) The Enantioselectivity in Oxazaborolidine-catalyzed Reductions of Phenyl Ethyl Ketone

Abstract

Abstract: The reaction mechanism of the enantioselectivity in oxazaborolidine catalyzed reductions of phenyl ethyl ketone has been studied by using AM1 method and transition state theory. The results show that the boron-catalyzed reactions consist of two similar parallel reactions in which the reactants(R) of the title compound and boron catalyst generate the enantiomers(P_R and P_S) via intermediate compounds IC(R) and IC(S) and transition states TS_R and TS_S, respectively. The enantioselectivity is determined by the ratio of the rate constants of two reactions. The value is 40 (that is R:S =97.5:2.5 or e.e. (R) =95%), which is in good consistence with experiment [exp. e.e. (R) =97(95)%]. The determining factors of the rate ratio come from the joint contribution of the activation enthalpy and activation entropy.

Key words: Phenyl ethyl ketone, Boron catalyzed, Enantioselectivity, AM1

CLC Number:

O641

TrendMD:

SUN Cheng-Ke, YANG Si-Ya, MA Si-Yu, LI Zong-He . Theoretical Studies on Asymmetric Boron-catalyzed Reaction(Ⅰ) The Enantioselectivity in Oxazaborolidine-catalyzed Reductions of Phenyl Ethyl Ketone[J]. Chem. J. Chinese Universities, 2002, 23(1): 109.

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Theoretical Studies on Asymmetric Boron-catalyzed Reaction(Ⅰ) The Enantioselectivity in Oxazaborolidine-catalyzed Reductions of Phenyl Ethyl Ketone

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