Photoinduced Cross-Coupling of Trifluoromethylarenes with Heteroarenes via Unactivated C(sp³)–F and C(sp²)–H Selective Cleavage

The installation of <i>gem</i>-difluoromethylene groups into two adjacent aryl groups is a formidable synthetic challenge despite their attractive structural, physical, and biochemical properties. Herein, we disclose a photoredox-catalyzed selective defluoroarylation of heteroarenes through inert C(sp³)-F and C(sp²)-H selective cleavage, which provides a straightforward route to access medicinally relevant aryl-heteroaryl or heteroaryl-heteroaryl difluoromethane scaffolds. Salient features of this reaction include readily accessible starting materials, metal-free conditions, and broad substrate scope.