DFT Studies on Copper-Catalyzed Arylation of Aromatic C–H Bonds

Abstract

Cu-catalyzed arylation of aromatic C–H bonds with phenyl iodide has been investigated with the aid of density functional theory calculations at the B3LYP level. Both the neutral and anionic catalytic cycles have been examined by considering the neutral (phen)­Cu–OMe and anionic [MeO–Cu–OMe]⁻ complexes, respectively, as the active species. Various heterocycle and polyfluorobenzene substrates were studied. The relationship between the overall reaction barrier and the acidity of the cleaved C–H bond was studied in both the neutral and anionic catalytic cycles. Comparing the overall reaction barriers based on the neutral and anionic catalytic cycles, we were able to understand that some substrates prefer the anionic mechanism while others prefer the neutral mechanism. We also examined how different ligands influence the overall barriers in the neutral catalytic cycles by employing <i>N</i>,<i>N</i>′-dimethylethylenediamine (DMEDA) and <i>N</i>-methylpyrrolidine-2-carboxamide as the ligands