Benzylic C(sp3)−H Alkoxylation through Visible‐Light‐Driven Oxidative Radical‐Polar Crossover

Abstract We report a metal‐free method for benzylic C(sp 3 )−H alkoxylation with a silyl ether as an alkoxylating agent. The reaction is considered to proceed through a sequence consisting of hydrogen atom transfer (HAT) and oxidative radical‐polar crossover, wherein Selectfluor serves as a one‐electron oxidant, a HAT agent, and a fluoride ion source. The fluoride ion formed in situ activates the silyl ether to give the alkoxide nucleophile, which reacts with a benzyl cation intermediate to provide the benzyl ether product. The present protocol has a broad substrate scope, enabling C−H alkoxylation of primary, secondary, and tertiary benzylic C(sp 3 )−H bonds. Furthermore, it is applicable for late‐stage C−H alkoxylation of bioactive molecules.