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Theoretical study of the C‐ vs. O‐Acylation of metal enolates. Frontier molecular orbital analysis including solvent effects
Author(s) -
Saragoni Victor G.,
Contreras Renato R.,
Aizman Arie J.
Publication year - 1993
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.560480863
Subject(s) - acylation , chemistry , reactivity (psychology) , molecular orbital , solvent , metal , computational chemistry , solvent effects , solvent polarity , polarity (international relations) , organic chemistry , molecule , medicine , biochemistry , cell , catalysis , alternative medicine , pathology
An extended version of the Klopman–Salem equation of chemical reactivity, which incorporates the effect of an external electrostatic field in both charge and orbital contributions, has been applied to analyze the reactivity pattern of ambident metal enolates towards acylation reactions in different solvents. The results are consistent with the experimental observation that the proportion of C‐acylation product is enhanced for solvents of low polarity where a relevant orbital control contribution is predicted. Comparison between the cis / trans proportion of C‐ and O‐acylation products are also qualitatively accounted for by the FMO analysis. © 1993 John Wiley & Sons, Inc.