Cyclic Hypervalent Iodine Reagents as a Bifunctional Platform for Benzylic C–H Oxidation via Dual Oxidative Radical–Polar Crossover

Comprehensive Summary The selective functionalization of unactivated benzylic C–H bonds in arenes and N ‐heteroarenes remains a pivotal challenge in synthetic chemistry, particularly for constructing oxygen‐containing functional groups with precision. Herein, we present an efficient photoredox‐catalysis strategy for the selective oxidation of benzylic C(sp 3 )–H bonds in both aromatic and N ‐heteroaromatic systems. This protocol employed cyclic hypervalent iodine reagents as a bifunctional platform functioning as hydrogen atom transfer (HAT) agent or radical precursor to facilitate the dual oxidative radical–polar crossover (ORPC) process under mild conditions, wherein water served as either a nucleophilic oxygen donor or quenching agent to initiate the oxidation process.