Palladium-catalyzed highly regioselective and stereoselective arylation of electron-rich allylamines with aryl bromides

Abstract A palladium-catalyzed, highly efficient Heck arylation of electron-rich N , N -diprotected allylamine derivatives with a wide range of aryl bromides under ligand-free conditions has been developed. In the presence of Pd(OAc) 2 and an appropriate additive, the reaction proceeds with excellent regioselectivity and stereoselectivity, leading exclusively to the γ-arylated ( E )-allylamine products in good to excellent yields. It was found that the choice of solvent, olefin, additive and temperature has an important influence on the reaction. Worthy of note is that good results were observed only when using N , N -diprotected allylamines containing carbamate moiety, and the steric properties of allylamines also have important impacts on the regiocontrol. The use of TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) or HQ (hydroquinone) as the additive is also crucial for securing a faster reaction rate. This method provides a straightforward approach for the efficient synthesis of various γ-arylated, linear ( E )-allylamines.