A Theoretical Study of The Ni-Catalyzed Reaction Aromatic Amides with Alkynes: C – O(Aryl) /N – H Annulation

Abstract

The mechanism of the reaction of amides with alkynes catalyzed by the nickel complex Ni(COD)2 was studied using the MN12L functional with 6-31G(d) basis sets for the main elements, and SDD with pseudo functions for the nickel atom by applying the SMD and PCM methods. The effect of various solvents (water, toluene, and DMSO) on the activation of the reaction was also studied. Computational results indicate that the SMD method with DMSO is the most energetically favorable, with a free energy barrier (DG) of about 8.5 kcal/mol, while the activation free energy (E^#) is about 15.7 kcal/mol for the TS(B-D) transition state associated with LiOPh group annulation as the rate-determining step. Furthermore, according to the PCM results, toluene is the most energetically favorable compared to the other solvents, with DG and E^# for the rate-determining step being about 18.1 kcal/mol and 22.0 kcal/mol, respectively. The global and local nucleophilic electrophilic indices of the reagents, as well as the topography of non-covalent interactions (NCI) and reduced density gradient (RDG) were analyzed.