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Computation Revealed a Case where Kinetic Selectivity is Controlled by Dynamics: Isomerization of Benzylideneanilines
Author(s) -
Cheettu Ammal Salai,
Yamataka Hiroshi
Publication year - 2006
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200600419
Subject(s) - isomerization , chemistry , conformational isomerism , selectivity , molecular dynamics , transition state , kinetic energy , potential energy surface , computational chemistry , ab initio , ab initio quantum chemistry methods , molecule , catalysis , organic chemistry , physics , quantum mechanics
The cis–trans isomerization of benzylideneaniline proceeds via a single transition state to afford two conformational isomers on the potential energy surface. Ab initio molecular dynamic simulations revealed that the observed kinetic selectivity of the two conformers for each of the cis and trans isomers is not governed by the relative stabilities of two independent transition states that would lead to the two conformers, respectively, but by the reaction dynamics. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)