β,γ-Vicinal Dicarbofunctionalization of Alkenyl Carbonyl Compounds via Directed Nucleopalladation.

A palladium(II)-catalyzed 1,2-dicarbofunctionalization reaction of unactivated alkenes has been developed, wherein a cleavable bidentate directing group is used to control the regioselectivity and stabilize the putative alkylpalladium(II) intermediate. Under the optimized reaction conditions, a broad range of nucleophiles and electrophiles were found to participate in this transformation, providing moderate to high yields. 3-Butenoic acid derivatives containing internal alkenes and α-substituents were reactive substrates, offering a powerful platform for preparing β,γ-substituted carbonyl compounds with multiple stereocenters.