Photoelectrochemical C−H Alkylation of Heteroarenes with Organotrifluoroborates

A photoelectrochemical method for the C?H alkylation of heteroarenes with organotrifluoroborates has been developed. The merger of electrocatalysis and photoredox catalysis provides a chemical oxidant‐free approach for the generation and functionalization of alkyl radicals from organotrifluoroborates. A variety of heteroarenes were functionalized using primary, secondary, and tertiary alkyltrifluoroborates with excellent regio‐ and chemoselectivity.