Sterically Controlled, Palladium-Catalyzed Intermolecular Amination of Arenes

We report the Pd-catalyzed amination of arenes to form N-aryl phthalimides with regioselectivity controlled predominantly by steric effects. Mono-, di-, and trisubstituted arenes lacking a directing group undergo amination reactions with moderate to high yields and high regioselectivities from sequential addition of PhI(OAc)(2) as an oxidant in the presence of Pd(OAc)(2) as catalyst. This sterically derived selectivity contrasts that for analogous arene acetoxylation.