Preparation of Benzolactams by Pd(OAc)2-Catalyzed Direct Aromatic Carbonylation

We developed a new method for Pd(II)-catalyzed direct aromatic carbonylation in a phosphine-free catalytic system using Pd(OAc)2 and Cu(OAc)2 in an atmosphere of CO gas containing air. The carbonylation proceeded with ortho-palladation, inducing a remarkable site selectivity to afford a variety of five- or six-membered benzolactams from secondary ω-arylalkylamines, such as N-alkylbenzylamines or N-alkylphenethylamines.