Intermolecular Insertion of Ethylene and Octene into a Palladium−Amide Bond. Spectroscopic Evidence for an Ethylene Amido Intermediate

摘要

Additions to olefins comprise some of the most utilized catalyticnreactions.n1nMany of these reactions occur by transfer of a hydride ornan alkyl group from a transition-metal complex to a coordinated alkenenin a reaction commonly termed migratory insertion.n2nMigratoryninsertion of an olefin into a transition metal amide bond is much lessnestablished but has been proposed to occur during several classes ofnpalladium-catalyzed reactions, including carboaminations,n3noxidativenaminations,n4ndiaminations,n5naminoacetoxylations,n6nchloroaminations,n7nand hetero-Heck type transformations.n8nStereochemical evidence fornsyn-aminopalladation by migratory insertion has been gained duringnstudies of some of these catalytic reactions,n3 6,9nbut intermolecularninsertion of an unactivated alkene into an isolated palladium amidoncomplex has not been reported.