Carboxylate Ligand-Exchanged Amination/C(sp3)-H Arylation Reaction via Pd/Norbornene Cooperative Catalysis

This report describes a carboxylate ligand exchange strategy that was used to achieve a Catellani reaction consisting of amination/unactivated aliphatic C-H arylation. Pivalic acid was used as an additive that could effectively promote C-H activation of unactivated alkanes without affecting the key five-membered aryl-norbornene-palladacycle (ANP) intermediate. Importantly, the reaction demonstrates high regioselectivity for the primary carbon. Following ortho-amination, the carboxylic acid was found to coordinate palladium in a bidentate fashion, and the pathway and driving force of carboxylic acid exchange was explored using density functional theory (DFT) calculations.