Pd-Catalyzed ligand-directed C—H functionalization has become one of the most important synthetic methods in organic chemistry. A theorecical study with the B3PW91 density functional theory method is carried out on Pd-catalyzed ligand-directed C—H acetoxylation. The thermodynamic properties in substrates binding step and C—H activation step are calculated. The data indicate that the selectivity of competition reactions between substrates with different directed group is determined by the substrates binding step. A larger complex stability constant will facilitate the formation of the corresponding product. However, the C—H activation step is unrelated to the reaction selectivity. Furthermore, no correlation is found between the reaction selectivities and the gas-phase basicities, Mulliken charges or HOMO energies of the directed groups.

Key words: ligand-directed, C—H bond acetoxylation, palladacycle, density functional theory (DFT)