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A DFT study of the enantioselective reduction of oxime ethers promoted by chiral spiroborate esters
Author(s) -
Qu Zhibo,
Chen Xiaolan,
Wei Donghui,
Ke Diandian,
Qu Lingbo,
Yuan Jinwei,
Bai Yunliang,
Wang Fujun,
Zhao Yufen
Publication year - 2011
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.23137
Subject(s) - chemistry , acetophenone , oxime , transition state , density functional theory , borane , computational chemistry , enantioselective synthesis , solvent , solvent effects , catalysis , reduction (mathematics) , medicinal chemistry , organic chemistry , geometry , mathematics
Mechanisms of borane reduction of the ( E )‐acetophenone O ‐methyl oxime catalyzed by the easily prepared and stable spiroborate ester 1, derived from diphenylvalinol has been reported for the first time using density functional theory. Two reaction pathways are investigated at the B3LYP/6‐31G(d,p) level of theory. The calculated results reveal that this reaction is accomplished via four steps. All the reactants, products, transition states, and intermediates have been optimized at the B3LYP/6‐31G (d,p) level. The analysis of these results reveals that one pathway is more energetically favorable than the other, and its associated product is in good agreement with the experimental result. The solvent effect has been further considered at the B3LYP/6‐31G(d,p) level in the solvent THF using the PCM model, and the results indicate that it has no great influence on the enantioselectivity of this reduction. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012