Photoelectrocatalytic heteroarene C(sp2)–H borylation

Abstract

Boryl radical-mediated C–H borylation remains underdeveloped due to challenges in the formation and control of boron-centered radicals. Herein, we report a photoelectrocatalytic strategy for direct C(sp²)–H borylation of (hetero)arenes using Lewis base–borane complexes under mild, external-oxidant-free conditions. The transformation proceeds via photoelectrochemically driven hydrogen atom transfer (HAT) catalysis mediated by anthraquinone-2-sulfonate (AQS), enabling efficient boryl radical generation without stoichiometric chemical oxidants. The resulting radicals undergo Minisci-type addition to protonated heteroarenes, affording heteroaryl boronates with broad substrate scope and excellent functional group tolerance.