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 beta-carbon atom. Mechanistic studies showed that the aminocarbonylation of the sigma-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.