Native Amine-Directed ortho-C–H Halogenation and Acetoxylation/Condensation of Benzylamines

Free or unfunctionalized benzylamines are well known to participate in C–H activation in the presence of palladium salts. Despite the ease with which these complexes can be activated, subsequent functionalization of the dimeric cyclometalates can be challenging. We demonstrate herein a free primary amine-based C–H activation/functionalization protocol that allows for the ortho-C–H chlorination and bromination of unprotected benzylamines. We also demonstrate how use of fluorine-based oxidants gives rise to a unique acetoxylation/cyclization owing to the nucleophilicity of the free primary amine directing group.