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A theoretical study on the mechanism of the baeyer–villiger type oxidation of 7-phosphanorbornene 7-Oxides

✍ Scribed by Attila Kovács; Dénes S. Nemcsok; György Keglevich

Publisher
John Wiley and Sons
Year
2007
Tongue
English
Weight
444 KB
Volume
18
Category
Article
ISSN
1042-7163

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✦ Synopsis

Abstract

DFT computations have been performed on selected stationary points of the reaction path (reactants, intermediates, and products) of the Baeyer–Villiger type oxidation of 7‐phosphanorbornene 7‐oxide derivatives. Our computations justified the relevance of a Criegee‐type intermediate forming in the first step, analogously to the Baeyer–Villiger oxidation of ketones. The energy profile indicated a high‐energy barrier from the side of the products, supporting the kinetic character of the mechanism. The computations revealed that the mechanism does not include a previously assumed Berry‐pseudorotation step in the Criegee‐type intermediate. On the basis of the present results, we suggest that the regioselectivity of the Baeyer–Villiger type oxidation of the 7‐phosphanorbornene 7‐oxide derivatives may be determined by steric interactions between the leaving meta‐chlorobenzoate group and substituents on the 7‐phosphanorbornene skeleton in the Criegee‐type intermediate. © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:759–766, 2007; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20366

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