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

Abstract Palladium‐catalyzed intramolecular carbopalladation of N‐aryl acrylamides followed by migratory insertion of an isocyanide‐coordinated C(sp 3 )−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.