A molecular electron density theory study of the mechanism, chemo- and stereoselectivity of the epoxidation reaction of R-carvone with peracetic acid

Abdellah Zeroual; Mar Ríos-Gutiérrez; Ouafa Amiri; Mohammed El Idrissi; Luis R Domingo

doi:10.1039/c9ra05309c

A molecular electron density theory study of the mechanism, chemo- and stereoselectivity of the epoxidation reaction of R-carvone with peracetic acid

RSC Adv. 2019 Sep 10;9(49):28500-28509. doi: 10.1039/c9ra05309c. eCollection 2019 Sep 9.

Authors

Abdellah Zeroual¹, Mar Ríos-Gutiérrez², Ouafa Amiri³, Mohammed El Idrissi^{1

4}, Luis R Domingo²

Affiliations

¹ Molecular Modeling and Spectroscopy Research Team, Faculty of Science, ChouaïbDoukkali University P.O. Box 20 24000 El Jadida Morocco.
² Department of Organic Chemistry, University of Valencia Dr. Moliner 50, 46100 Burjassot Valencia Spain domingo@utopia.uv.es.
³ Laboratory of Organic and Analytical Chemistry, Faculty of Sciences and Techniques, Sultan Moulay Slimane University B. P. 523 Beni-Mellal Morocco.
⁴ Department of Chemistry, Polydisciplinary Faculty, Sultan Moulay Slimane University Beni-Mellal Morocco.

Abstract

The epoxidation reaction of R-carvone 8 with peracetic acid 9 has been studied within the molecular electron density theory at the B3LYP/6-311(d,p) computational level. The chemo- and stereoisomeric reaction paths involving the two C-C double bonds of R-carvone 8 have been studied. DFT calculations account for the high chemoselectivity involving the C-C double bond of the isopropenyl group and the low diastereoselectivity, in complete agreement with the experimental outcomes. The Baeyer-Villiger reaction involving the carbonyl group of R-carvone 8 has also been analysed. A bonding evolution theory analysis of the epoxidation reaction shows the complexity of the bonding changes taking place along this reaction. Formation of the oxirane ring takes place asynchronously at the end of the reaction by attack of anionic oxygen on the two carbons of the isopropenyl C-C double bond.