Carboxylate-assisted oxidative addition to aminoalkyl-Pd(II) complexes enables catalyzed C(sp3)-H arylation of alkylamines via distinct Pd(II)/Pd(IV) pathway.

Reported is the discovery of an approach to functionalize secondary alkylamines using 2-halobenzoic acids as aryl-transfer reagents. These reagents promote an unusually mild carboxylate-assisted oxidative addition to alkylamine-derived palladacycles. In the presence of Ag-I salts, a decarboxylative C(sp(3))-C(sp(2)) bond reductive elimination leads to g-aryl secondary alkylamines and renders the carboxylate motif a traceless directing group. Stoichiometric mechanistic studies were effectively translated to a Pd-catalyzed gamma-C(sp(3))-H arylation process for secondary alkylamines.