Palladium‐Catalyzed Imidoylative Cyclization of α‐Isocyanoacetamides: Efficient Access to C2‐Diversified Oxazoles

A novel procedure for the synthesis of C2‐diversified oxazoles, through palladium‐catalyzed imidoylative cyclization of α‐isocyanoacetamides with aryl, vinyl, alkynyl halides, or triflates, was developed. Migratory insertion of isocyanide into a C   sp   3‐palladium(II) intermediate in a cascade process was also realized, generating alkyl‐substituted oxazoles. Therefore, oxazoles functionalized at the C2 position with sp, sp 2 , and sp 3 hybridized carbon atoms are accessible by applying this method.