Stereoselective palladium-catalyzed oxidative C–N bond coupling reactions between aromatic amines and alkenes involving a solvent-controlled regioselective bromination process under 1 atm of oxygen atmosphere are disclosed, providing easy access to two different brominated enamines. The addition of hydrogen peroxide (30% aq) as a co-oxidant in the system is crucial for the dehydrogenative aminohalogenation under molecular ...