Abstract
Density functional theory (DFT) calculations were conducted to elucidate the mechanism of a novel Pd(II) catalyzed C(sp3)–H activation and the subsequent arylation reactions of amides in the presence of pyridine derivatives as ligands. All plausible pathways were carefully studied, and the minimum energy pathway was located successfully. Being different from most of the C–H activation reactions, 2-picoline used in this reaction reacts with Pd(TFA)2 (trifluoroacetate) to form a very stable precatalyst. Measures should thus be taken to activate the precatalyst, including the modification of the amide substrate and a proper choice of solvent. Our calculations helped to reveal the relevant details. An unconventional deprotonation mechanism for the C–H activation step, which is different from the traditional CMD (or AMLA) mechanism, was found through our theoretical studies. The methyl group is deprotonated by an out-of-plane (external) TFA, rather than a TFA ligand directly bound to the Pd(II) atom. As part o...
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