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.