Visible-Light-Driven Copper-Catalyzed C(sp3)-O Cross-Coupling of Benzylic Radicals with Phenols.

A visible-light-driven, copper-catalyzed C(sp3)-O coupling of benzylic radicals with phenols is described for the first time. This operationally simple and robust process features mild conditions, broad scope, and high functional-group tolerance, enabling the construction of a diverse range of cyanoalkylated aryl ethers (33 examples). Key to this protocol is the dual role of copper salt that acts not only as a photosensitizer but also as a cross-coupling catalyst.