Palladium-Catalyzed 2-Aminoacetophenone Oxime Directed β-sp2 and γ-sp3 C―H Bond Functionalization of Aryl Carboxamides

Pd(II)-catalyzed 2-aminoacetophenone oxime-assisted sp(2) and sp(3) C & horbar;H arylation of aryl carboxamides is disclosed. The 2-aminoacetophenone oxime is an N,N-bidentate auxiliary that proceeds C & horbar;H activation through a six-membered palladacycle intermediate, and the activation/functionalization on C(sp(3))& horbar;H bond by the six-membered ligand palladacycle is novel and achieved. This auxiliary facilitates the subsequent sp(3) and sp(2) C & horbar;H bond activation/functionalization in one step. The optimized protocol enables access to various aryl groups at the beta-sp(2)- and gamma-sp(3)-centers of aryl carboxamides. The bidentate auxiliary is easy to synthesize on a gram scale, and we also described deoximination procedure after C & horbar;H functionalization.