Theoretical study on the copper-catalyzed asymmetric alkene trifluoromethyl–arylation cross-coupling reaction: origin of regio- and stereo-selectivity

Abstract

To examine the mechanism and origin of regio- and stereo-selectivity, density functional theory calculations were employed for the Cu-catalyzed asymmetric alkene trifluoromethyl–arylation cross-coupling reaction. Theoretical studies reported that this reaction proceeded via single electron transfer, radical addition, transmetallation, one-electron oxidation, and reductive elimination. The stereoselectivity of this reaction was determined by the one-electron oxidation step. Independent gradient model calculations were employed to investigate the origin of stereoselectivity established using the chiral dioxazoline ligand. Furthermore, the substituent effects of the alkene substrate were calculated. This study aims to serve as a theoretical framework for future experimental investigations on the alkene difunctionalization cross-coupling reaction.