Intermolecular 1,2‐Difunctionalization of Nitriles via Redox Gold Catalysis: Synthesis of Benzoxazoles and Benzimidazoles

The unprecedent gold‐catalyzed intermolecular 1,2‐difunctionalization of nitriles with aryl iodides via Au(I)/Au(III) redox catalysis has been developed, providing an expedient route to the synthesis of benzoxazoles and benzimidazoles with broad substrate scope and high functional compatibility. Mechanistic investigation reveals that the Au(III)‐Ar species generated via oxidative addition of o‐iodophenol to MeDalphosAu+, serves as a key intermediate. Particularly and this annulation is initiated by oxidative addition, rather than the nucleophilic attack of the phenol moiety in o‐iodophenol towards the nitrile. The method was also applied to the synthesis of poly aza‐heterocycles via a cascade Au(I)/Au(III) and Au(I) catalysis relay.