Au(I)/Au(III)-Catalyzed Annulative Addition of Alkynes to Aryl Iodides

We present a ligand-enabled, gold-catalyzed <i>syn</i>-1,2-carbohetero-functionalization of both internal and terminal alkynes with <i>o</i>-iodo-arylamides. The transformation integrates a tandem oxidative addition and <i>syn</i>-auration, affording a diverse array of <i>syn</i>-carbohetero-functionalization products in yields of up to 95%. Distinct from the <i>anti</i>-addition typically observed in intermolecular gold catalysis, the involvement of intramolecular annulative cyclization dictates a selective <i>syn</i>-addition pathway. Leveraging Au(I)/Au(III) redox catalysis, this strategy establishes a distinct cyclization strategy that exhibits excellent functional-group tolerance and enables late-stage modification of complex pharmaceutical scaffolds.