Implicit and explicit solvent effects on the selectivity of the cycloaddition reaction of cyclopentadiene and methyl acrylate; a theoretical study

The product selectivity of the Diels-Alder reaction between cyclopentadiene and methyl acrylate has been studied through a solvent effect analysis by implicit and explicit solvent models. Two paths for this reaction have been proposed and thermodynamic and kinetic parameters for each path were calculated by the B3LYP functional with 6-311++G(d,p) basis set at 298.15 K. In the explicit solvent model, hydrogen bonds were investigated by the QM/MM method. According to the results, the proportion of the exo product in the gas phase is more than for the endo one, which is in contrast to the solvent phase. HOMO-LUMO analyses in the gas phase and different solvents have been done and solvent effects on the energies of the HOMO-LUMO orbitals were investigated. According to the results, the band gap of the TSs was increased in the presence of the solvents. Finally, natural population analysis has been performed to calculate the electronic charges of some atoms that are involved in the centre of the reaction. The data obtained showed that different solvents, including polar and nonpolar solvents, have different effects on the electronic charges of the atoms. Topological analysis of the structures during the reaction by the quantum theory of atoms in molecules (QTAIM) method in the gas phase and different solvents confirmed a cyclic structure for the transition state.