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DFT study of the asymmetric nitroaldol (Henry) reaction catalyzed by a dinuclear Zn complex
Author(s) -
Qi Na,
Liao RongZhen,
Yu JianGuo,
Liu RuoZhuang
Publication year - 2010
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21422
Subject(s) - nitromethane , nitroaldol reaction , deprotonation , catalysis , chemistry , protonation , alkoxide , density functional theory , computational chemistry , catalytic cycle , enantioselective synthesis , ion , organic chemistry
We report the mechanism of asymmetric nitroaldol (Henry) reaction catalyzed by a dinuclear Zn complex using density functional theory. The experimentally proposed catalytic cycle is validated, in which the first step is the deprotonation of nitromethane by the ethyl anion of the catalyst, subsequently a CC bond formation step, and then the protonation of the resulting alkoxide. Three mechanistic scenarios (differing in binding modes) have been considered for the CC bond formation step. The origin of the enantioselectivity is discussed. Our calculations supported that the S configurations are the major products, which is in agreement with the experimental observations. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010