Substrate and CatalystCocontrolled Regioselectiveand Chemo-Switchable Annulation of Unsymmetric Cyclic AryIiodoniums

Cyclic aryliodoniums are widely used as arylative reagents via a ring opening process. Despite the numerous synthetic achievements, the precise control of the regioselective ring opening of unsymmetrical cyclic aryliodoniums remains a fundamental challenge in synthetic chemistry. Herein, we report an effective substrate and catalyst cocontrolled regioselective and chemoselective ring opening and reclosing of cyclic aryliodoniums with alkynes. Particularly, <i>ortho</i>-installed aryliodonium amido groups and palladium catalysts direct the switch of the formation of either C–N or C–O bond during the annulation. The control experiment and density functional theory (DFT) study indicate the cooperative mode influenced by the steric and electronic effects of the substrates and catalysts. This method features broad substrate scope, good functional compatibility, and high chemoselectivity, providing divergent tetra-heterocyclic arenes. It further demonstrated the practicality of this protocol with complex substrates derived from a series of clinical drugs in high efficiency.