Synthesis of Amides and Esters by Palladium(0)‐Catalyzed Carbonylative C(sp3)−H Activation

Abstract The 1,4‐palladium shift strategy allows the functionalization of remote C−H bonds that are difficult to reach directly. Reported here is a domino reaction proceeding by C(sp 3 )−H activation, 1,4‐palladium shift, and amino‐ or alkoxycarbonylation, which generates a variety of amides and esters bearing a quaternary β‐carbon atom. Mechanistic studies showed that the aminocarbonylation of the σ‐alkylpalladium intermediate arising from the palladium shift is fast using PPh 3 as the ligand, and leads to the amide rather than the previously reported indanone product.