Photoelectrochemical Dehydrogenative Cross-Coupling of Aliphatic C–H Bonds via an In-Situ-Generated Hypervalent Iodine Mediator

A photoelectrochemical strategy is disclosed for the first time that allows for the in-situ generation of hypervalent iodine species I(III) via anodic oxidation, followed by photolytic formation of a trifluoroethoxy radical. This alkoxy radical undergoes hydrogen atom transfer (HAT) with aliphatic C(sp 3 )–H bonds to generate alkyl radicals, which are then captured by various trapping agents. This metal- and chemical-oxidant-free system operates under mild conditions, exhibits broad substrate scope and gram-scale scalability, and expands the utility of aryl iodides in photoelectrochemical synthesis.