Abstract: | A general and convenient palladium‐catalyzed oxidative Heck arylation of both N‐protected and N,N‐diprotected allylic amines with arylboronic acids under mild conditions has been developed. The catalyst system, consisting of Pd(OAc)2 (palladium acetate), AgOAc (silver acetate) and KHF2 (potassium hydrogen fluoride), could efficiently catalyze the coupling reaction in acetone without the aid of any ligand, leading exclusively to the γ‐arylated allylic amine products in good to excellent yields. This method is highlighted with excellent regio‐ and stereocontrol and remarkable functional group tolerance. The carbamate moiety in allylic amine substrates is of crucial importance to the catalytic performance, and the chelation between the carbonyl O (oxygen) and Pd (palladium) atoms is believed to be responsible for the high regioselectivity and stereoselectivity observed. |