The Pd-catalyzed C-H alkylation of ortho-methyl-substituted aromatic amides with maleimide occurs preferentially at the ortho-methyl C-H bond over the ortho-C-H bond

The reaction of ortho-methyl-substituted aromatic amides with maleimides in the presence of Pd(OAc) and AgOAc results in C-H alkylation at the ortho-methyl C-H bond. DFT calculations indicate that the formation of a five-membered palladacycle is a kinetically favorable step, but the insertion of the maleimide into the six-membered palladacycle is energetically favored.