A Dft Study of Solvent Effects on the Cycloaddition of Norbornadiene and 3,4–Dihydroisoquinoline-N-Oxide

Abstract

A theoretical study of the kinetics and mechanism of the second-order inter-molecular cycloaddition of norbornadiene and 3,4-dihydroisoquinoline-N-oxide (nitrone) at 398.15 K was performed using the DFT method at the B3LYP level of theory with the 6–311++G(d,p) basis set. Equilibrium molecular geometries and harmonic vibrational frequencies of the reactants, transition state and product were calculated. The effect of solvents on the kinetic and thermodynamic parameters of the reaction were investigated. The calculated rate constants and activation parameters showed very good agreement with experimental results, especially for ethanol as solvent. These calculations indicated that the reaction proceeds through a synchronous concerted mechanism.