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A density functional theory study of the enantioselective reduction of prochiral ketones promoted by chiral spiroborate esters
Author(s) -
Wei Donghui,
Tang Mingsheng,
Zhang Wenjing,
Zhao Jing,
Sun Ling,
Zhao Chufeng,
Wang Homgming
Publication year - 2010
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.22307
Subject(s) - chemistry , density functional theory , enantioselective synthesis , borane , pyrrolidine , transition state , computational chemistry , catalysis , reduction (mathematics) , solvent , solvent effects , organic chemistry , geometry , mathematics
Recently, chiral spiroborate ester [( R )‐2‐((1,3,2‐dioxaborolan‐2‐yloxy)methyl)pyrrolidine] has been experimentally employed as an effective chiral catalyst in the borane‐mediated asymmetric reduction of prochiral ketones to produce the corresponding secondary alcohols. In this article, we have theoretically investigated the mechanism of the reduction using density functional theory. The results reveal that this reaction is accomplished via four steps. Fully geometry optimized reactants, products, transition states, and intermediates were obtained at the B3LYP/6‐31G (d, p) level. The analysis of these results reveals one pathway that is more energetically favorable, and its associated geometries correlate well with the final products of the reaction. The further calculations show that the solvent effect of THF has no great influence on enantioselectivity of this reduction. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010