Theoretical Chemistry Accounts

, Volume 112, Issue 4, pp 290–297 | Cite as

Acid-catalysed oxidative ring-opening of epoxide by DMSO. Theoretical investigation of the effect of acid catalysts and substituents

Article

Abstract.

DFT studies have been carried out in order to investigate the reaction mechanism of a series of acid-catalysed oxidative ring-opening of epoxides in DMSO. The role of the acid catalyst during the oxidation of ethylene oxide has been investigated by employing three acids, namely H3O+, Li+, and Mg2+. Effects of substituents on the epoxide have been investigated by including butene oxide and cyclopentene oxide as the reacting species. Stationary points have been obtained at the B3LYP/6–31++G(d,p) level of theory and the reaction barriers have been evaluated through free-energy calculations. This is the first mechanistic elucidation for such a process, involving oxidation of the epoxide ring by DMSO. The mechanism proceeds in two steps, namely a ring-opening step followed by an intramolecular proton transfer which leads to an α-hydroxyketol. The results show that the second step is the energetically less favourable, a feature consistent with the harsh experimental conditions needed to obtain such products. The role of the acid catalyst is discussed and we show that use of H3O+ or Mg2+ as an activator leads to similar results concerning the reaction energetics.

Keywords

Density functional theory Epoxide Ring-opening Lewis acid-catalyst Reaction mechanisms 

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Notes

Acknowledgements.

J. Golebiowski and S. Antonczak seize the opportunity of this special issue to gratefully thank Pr. Jean-Louis Rivail for the great years spent in his laboratory.

Copyright information

© Springer-Verlag Berlin Heidelberg 2004

Authors and Affiliations

  1. 1.Laboratoire Arômes Synthèses InteractionsFaculté des Sciences, Université de Nice Sophia-Antipolis Nice Cedex 2France

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