A theoretical study on the mechanism of the Baeyer-Villiger type oxidation of 7-phosphanorbornene 7-oxides

Attila Kovács, Dénes S. Nemcsok, G. Keglevich

Research output: Contribution to journalArticle

3 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)759-766
Number of pages8
JournalHeteroatom Chemistry
Volume18
Issue number7
DOIs
Publication statusPublished - 2007

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Oxides
Oxidation
Derivatives
Regioselectivity
Energy barriers
Ketones
Discrete Fourier transforms
Kinetics
3-chlorobenzoic acid

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

A theoretical study on the mechanism of the Baeyer-Villiger type oxidation of 7-phosphanorbornene 7-oxides. / Kovács, Attila; Nemcsok, Dénes S.; Keglevich, G.

In: Heteroatom Chemistry, Vol. 18, No. 7, 2007, p. 759-766.

Research output: Contribution to journalArticle

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