The mechanisms of the rhodium-catalyzed cycloaddition of 2-vinylphenol with diphenylacetylene and carbon monoxide have been studied using density functional theory calculations at the B3LYP/6-31G (d, p) (Lanl2dz for Rh) level of theory. The SMD solvation model was used in MeCN solvents at M06-2X/6-311 ++ G (d, p) (Lanl2dz (f) for Rh) levels using a single-point calculation to consider the solvent effect. The calculation results show that there are two competitive reaction pathways for the cycloaddition reaction of rhodium-catalyzed synthesis of benzohexine and coumarin. Starting from the precursor reaction complex, the reaction channel is more favorable for the carbon atoms of diphenylacetylene and carbon monoxide to attack the Rh-C bond (the barriers of 9.88 and 10.01 kcal/mol) rather than attack the Rh-O bond (the barriers of 15.37 and 30.17 kcal/mol), and carbon monoxide in two different reaction channels has a greater energy difference than diphenylacetylene. The results show that the computational study of the rhodium-catalyzed cycloaddition reaction has a high catalytic activity consistent with the high yield of the experiment of Gulías et al.
Keywords: 2-vinylphenol; Cycloaddition; Diphenylacetylene; Rhodium(III)-catalyzed.