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

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(sp3)−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 PPh3 as the ligand, and leads to the amide rather than the previously reported indanone product. Amides and esters bearing a quaternary β‐carbon atom are synthesized by a domino reaction involving C(sp3)−H activation, 1,4‐Pd shift, and amino/alkoxycarbonylation. Mechanistic studies showed that the aminocarbonylation of the σ‐alkylpalladium intermediate arising from the palladium shift is fast, and leads to the amide rather than the previously reported indanone product.