Mechanistic Insight into Palladium/Brønsted Acid Catalyzed Methoxycarbonylation and Hydromethoxylation of Internal Alkene: A Computational Study

Abstract

Density functional theory (DFT) calculations were performed to study the palladium/Brønsted acid-catalyzed methoxycarbonylation and hydromethoxylation reactions of internal alkene. The calculated results show that the pyridyl group (N atom) in bidentate phosphine ligand with built-in base (L1) plays a crucial role in controlling the selectivity. With the help of the pyridyl group, the methanolysis steps in the methoxycarbonylation reaction and the hydromethoxylation reaction become easy, and both the linear ester methyl 3,4-dimethylpentanoate (P1) and the hydromethoxylation product 2-methoxy-2,3-dimethylbutane (P2) could be obtained. In contrast, the possibility of leading to branched ester P1′ was ruled out according to our calculations. The steric effect could account for the observed selectivity. In the presence of the DPEphos ligand (L2) that does not bear the pyridyl group, the methanolysis step in the methoxycarbonylation reaction becomes the rate-determining step with a high overall energy barrier. Neither linear nor branched methoxycarbonylation product could be generated. The palladium/Brønsted acid co-catalyzed hydromethoxylation also become difficult without the assistance of the pyridyl group in the presence of the L2 ligand. Instead, TsOH-catalyzed hydromethoxylation reaction could take place to generate the ether product P2.