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

摘要

Palladium-catalyzed intramolecular carbopalladation of N-aryl acrylamides followed by migratory insertion of an isocyanide-coordinated C(sp(3))-Pd intermediate afforded an alkylimidoyl-PdII complex, which can be intercepted by a nucleophile, including heteroarenes. In addition to amides, the alkylimidoyl-PdII complex was successfully converted into esters, ketones, and bis-heterocyclic compounds. An unprecedented palladium-catalyzed enantioselective domino process involving isocyanide was also documented.