DFT study on α-regioselectivity of photo-organocatalytic functionalization of aldehydes

Abstract

Density functional theory (DFT) study has been conducted to elucidate the key mechanistic transformations and the unique α-regioselectivity of alkylidene malonates towards the photoinitiated α-alkylation of aldehydes. The reaction between n-butyl aldehyde and diethyl methylenemalonate was chosen as model reaction and the possible reaction pathways were computed. Our calculations reveal that α-alkylation of aldehydes with alkylidene malonates proceeds through a radical–radical coupling pathway, instead of the radical chain or radical propagation pathway. This work demonstrates the details of the mechanistic framework and rationalizes the α-regioselectivity of alkylidene malonates.