| The catalytic carbonylation reaction is one of the most important applications of homogenous catalysts. Many catalytic carbonylation processes of alkynes are activated using complexes of nickel, palladium, and platinum with phosphine ligands. Different products can be formed from the carbonylation reactions depending on the type of the nucleophile. Recently, the Pd-catalytic carbonylation reaction of terminal alkynes conducted with aniline forms gem- and trans-alpha,beta-unsaturated amides with a total control of the regioselectivity under certain reaction conditions. The products' distribution (regioselectivity) was affected by the variation of the experimental conditions of the catalytic systems. The explanation of the detailed mechanism of this palladium carbonylation process is not developed yet. Theoretical calculations provide the best approach to reveal the detailed mechanism of this catalytic process.; In this study, density function calculations have been carried out to investigate the mechanism of this catalytic carbonylation process. The computed results show that an oxidative-addition mechanism with the possibility of phosphine ligand to coordinate/decoordinate over the process is the major pathway of the process that use syngas (CO/H2) and terminal alkyne. Several experiments were performed to test the proposed reaction routes and the rate-determining step. |
