Palladium-catalyzed 3,4-hydroaminocarbonylation of conjugated dienes for formation of β,γ-unsaturated amides

Hydrocarbonylation of conjugated dienes is one of the most promising yet challenging methods for the synthesis of carbonyl compounds. Herein, we reported the development of an unprecedented palladium-catalyzed branched selective 3,4-hydroaminocarbonylation of 1,3-dienes with CO and amines hydrochloride to afford beta,gamma-unsaturated amides. This reaction employs readily available starting materials (including anilines, amines, amino acids, peptides, aryl-1,3-dienes, alyl-1,3-dienes) and tolerates a wide range of functional groups, thus providing a facile and effective approach to access a diverse array of alpha-substituted beta,gamma-unsaturated amides. Mechanistic investigations suggested that the hydropalladation of dienes is irreversible, and the insertion of CO into the allyl-Pd species is probably the rate-limiting step.