Carboxylate-Assisted Oxidative Addition to Aminoalkyl PdII Complexes: C(sp3 )-H Arylation of Alkylamines by Distinct PdII /PdIV 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 AgI salts, a decarboxylative C(sp3 )-C(sp2 ) bond reductive elimination leads to γ-aryl secondary alkylamines and renders the carboxylate motif a traceless directing group. Stoichiometric mechanistic studies were effectively translated to a Pd-catalyzed γ-C(sp3 )-H arylation process for secondary alkylamines.