Visible‐Light‐Induced Vicinal Dichlorination of Alkenes through LMCT Excitation of CuCl2

Abstract This work demonstrates photoredox vicinal dichlorination of alkenes, based on the homolysis of CuCl 2 in response to irradiation with visible light. This catalysis proceeds via a ligand to metal charge transfer process and provides an exciting opportunity for the synthesis of 1,2‐dichloride compounds using an inexpensive, low‐molecular‐weight chlorine source. This new process exhibits a wide substrate scope, excellent functional group tolerance, extraordinarily mild conditions and does not require external ligands. Mechanistic studies show that the ready formation of chlorine atom radicals is responsible for the facile formation of C−Cl bonds in this synthetic process.