Synthesis of Diversely Functionalized Oxindoles Enabled by Migratory Insertion of Isocyanide to a Transient σ-Alkylpalladium(II) Complex

Palladium-catalyzed intramolecular carbopalladation of N-aryl acrylamides followed by migratory insertion of an isocyanide-coordinated C(sp3)-Pd intermediate afforded an alkylimidoyl-Pd(II) complex, which can be intercepted by a nucleophile, including heteroarenes. In addition to amides, the alkylimidoyl-Pd(II) complex was successfully converted into esters, ketones, and bis-heterocyclic compounds. An unprecedented palladium-catalyzed enantioselective domino process involving isocyanide was also documented.