Direct C(sp³)–H Cross Coupling Enabled by Catalytic Generation of Chlorine Radicals

Here we report the development of a C(sp³)-H cross-coupling platform enabled by the catalytic generation of chlorine radicals by nickel and photoredox catalysis. Aryl chlorides serve as both cross-coupling partners and the chlorine radical source for the α-oxy C(sp³)-H arylation of cyclic and acyclic ethers. Mechanistic studies suggest that photolysis of a Ni(III) aryl chloride intermediate, generated by photoredox-mediated single-electron oxidation, leads to elimination of a chlorine radical in what amounts to the sequential capture of two photons. Arylations of a benzylic C(sp³)-H bond of toluene and a completely unactivated C(sp³)-H bond of cyclohexane demonstrate the broad implications of this manifold for accomplishing numerous C(sp³)-H bond functionalizations under exceptionally mild conditions.