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On the Origin of Altered Diastereomeric Ratios for Anionic versus Neutral Reaction Conditions in the Oxy‐Cope/Ene Reaction: An Interplay of Experiment and Computational Modeling
Author(s) -
Hooper James,
Sauer Effiette L. O.,
Arns Steve,
Woo Tom K.,
Barriault Louis
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201001302
Subject(s) - isomerization , chemistry , ab initio , reaction mechanism , potential energy surface , ene reaction , olefin fiber , computational chemistry , molecular dynamics , diastereomer , potential energy , ab initio quantum chemistry methods , catalysis , stereochemistry , molecule , organic chemistry , physics , quantum mechanics
We report herein a detailed investigation into the reaction mechanism for a sequential oxy‐Cope/ene reaction under anionic conditions. With DFT calculations and ab initio molecular dynamics simulations, the observed diastereoselectivity is shown to be the result of an isomerization of the enolate olefin, which would evidently not occur under neutral conditions. The potential energy surface was thoroughly mapped out for the reaction pathways and the proposed mechanism confirmed the different product distributions observed under neutral and anionic oxy‐Cope conditions. In addition, other possible pathways are shown to be higher in energy and experimental evidence is given that supports the olefin‐isomerization pathway.