Palladium-Catalyzed Transfer Iodination from Aryl Iodides to Nonactivated C(sp3)–H Bonds

We report a new strategy for the catalytic iodination of nonactivated C(sp3)-H bonds. The method merges the concepts of shuttle and light-enabled palladium catalysis to employ aryl iodides as both hydrogen atom transfer reagents and iodine donors. A noncanonical Pd0/PdI catalytic cycle is harnessed to transfer iodine from a C(sp2) to a C(sp3)-H bond under mild conditions, which tolerate sensitive functional groups. This mechanism is also applied to implement a C(sp3)-H thiolation that exploits reversible steps of the system.