Palladium‐Catalyzed 2‐Aminoacetophenone Oxime Directed <i>β</i>‐sp² and <i>γ</i>‐sp³ C─H Bond Functionalization of Aryl Carboxamides

Abstract Pd(II)‐catalyzed 2‐aminoacetophenone oxime‐assisted sp 2 and sp 3 C─H arylation of aryl carboxamides is disclosed. The 2‐aminoacetophenone oxime is an N,N ‐bidentate auxiliary that proceeds C─H activation through a six‐membered palladacycle intermediate, and the activation/functionalization on C(sp 3 )─H bond by the six‐membered ligand palladacycle is novel and achieved. This auxiliary facilitates the subsequent sp 3 and sp 2 C─H bond activation/functionalization in one step. The optimized protocol enables access to various aryl groups at the β ‐sp 2 ‐ and γ ‐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─H functionalization.