Visible-Light-Induced Alkoxyl Radical Generation Enables Selective C(sp3)–C(sp3) Bond Cleavage and Functionalizations

The alkoxyl radical is an important reactive intermediate in mechanistic studies and organic synthesis; however, its current generation from alcohol oxidation heavily relies on transition metal activation under strong oxidative conditions. Here we report the first visible-light-induced alcohol oxidation to generate alkoxyl radicals by cyclic iodine­(III) reagent catalysis under mild reaction conditions. The β-fragmentation of alkoxyl radicals enables selective C­(sp3)–C­(sp3) bond cleavage and alkynylation/alkenylation reactions with various strained cyclo­alkanols, and for the first time with linear alcohols.