Photoelectrocatalytic Chlorothiocyanation of Unactivated Alkenes via Ligand-to-Metal Charge Transfer

The difunctionalization of unactivated alkenes has widespread applications in organic synthesis. However, the selective introduction of two different functional groups remains challenging. We herein report a photoelectrochemical chlorothiocyanation of unactivated alkenes via an Fe-catalyzed ligand-to-metal charge transfer (LMCT) process. The generation of electrophilic thiocyanate radical from an FeIII-SCN complex under mild LMCT conditions is realized for the first time. This protocol provides a platform to install two versatile functional groups (SCN and Cl) selectively with a broad substrate scope.