Asymmetric reductive carboxylation of N-(2-bromophenyl)-N-methylmethacrylamide with CO₂ catalyzed by nickel complex: A theoretical study

To provide guiding information for developing efficient catalysts for CO2 carboxylation, we investigated the mechanism of asymmetric reductive carboxylation of N-(2-bromophenyl)-N-methylmethacrylamide with CO2 catalyzed by a nickel complex using density functional theory (DFT) calculations. The reaction was found to proceed via a multistep and elaborate mechanism. Additionally, CO2 exhibits a preference for inserting into the Ni(I) intermediate rather than Ni(II) intermediate. The noncovalent interaction (NCI) analysis reveals that the pi-pi stacking interactions and hydrogen bonding interactions lead to the stereoselectivity.