Cationic, Iodine(III)‐Mediated and Directed Diastereoselective Oxidation of Inert C−H Bonds in Cyclic Hydrocarbons

Abstract Over the past three decades, the functionalization of unactivated C−H bonds has become a workhorse of synthesis. In the field of C−H bond oxygenation, most established methods hinge on single‐electron reactivity, encountering challenges pertaining to regio‐ and/or stereocontrol. Herein, we describe a conceptually distinct strategy relying on the unique features of carbocation chemistry. Our iodine(III)‐mediated method achieves the diastereoselective oxygenation of remote C−H bonds at traditionally unreactive sites and enables late‐stage functionalization at steroidal frameworks as well as an unusual chirality relay.