Chloride‐Promoted Photoelectrochemical C—H Silylation of Heteroarenes†

Comprehensive Summary A photoelectrochemical approach for the C—H silylation of heteroarenes through dehydrogenation cross‐coupling with H 2 evolution has been developed. The photoelectrochemical C—H silylation depends on hydrogen atom transfer (HAT) from silanes to Cl‐radical generated through the light‐induced homolytic cleavage of Cl 2 , in which Cl 2 was produced by electrochemical oxidation of chloride. A large number of silylated heterocyclic molecules are rapidly constructed in satisfactory yields without relying on oxidants and metal reagents.