Visible-Light-Induced Oxidative α-keto-Dichlorination of Arylalkynes by CuCl2 at Room Temperature

Abstract

A visible light-induced oxidative α-keto-dichlorination of terminal and internal aryl alkynes was developed to form dichloroacetophenones (DCAPs) and dichlorophenyl-acetophenones (DCPAPs), respectively, by using CuCl2 as a photoredox catalyst in the presence of air at room temperature (without using any exogenous photocatalyst). Here, photoexcited CuCl2 underwent ligand-to-metal charge transfer to generate a Cl radical, which readily added to the alkynes to form DCAPs or DCPAPs in the presence of O2. This α-keto-dichlorination reaction is a green and mild protocol as it produced water as the only by-product. Moreover, the evaluation of green chemistry metrics indicated that the E-factor (mass of wastes/mass of products) of the current α-keto-chlorination method is around 10.1 times lower than that of a literature-reported photochemical method. The Eco Scale value (score 55, which on a scale of 0–100 indicates an acceptable synthesis) signifies that this process is simple, highly efficient, eco-friendly, and cost-effective.