Palladium-Catalyzed Amide-Directed Hydrocarbofunctionalization of 3-Alkenamides with Alkynes

A Pd-catalyzed carboxamide-directed hydrocarbofunctionalization reaction of unactivated alkenes with different alkynes has been developed. An 8-aminoquinoline auxiliary was utilized to increase the reactivity of the alkene and control the regioselectivity via the formation of thermodynamically favored five-membered palladacycle intermediate. 3-Alkene carboxamides bearing a C4-substituted alkene group reacted with a variety of terminal alkynes in the presence of an ortho-phenyl benzoic acid promoter, yielding ?-alkynylated products with high yields and regioselectivity. 3-Butenamide underwent a three-component coupling reaction with internal alkynes and carboxylic acids to give vinyl ester products. Preliminary mechanistic studies indicate that the intramolecular migratory insertion of alkynyl or vinyl palladium species into the C=C bond is responsible for the gamma-selective alkynylation or alkenylation of the alkene group.