Effect of an α-Methyl Substituent on the Dienophile on Diels-Alder endo:exo Selectivity

Abstract

A detailed computational study of the Diels-Alder reaction of cyclopentadiene with acrylonitrile, methylacrylate and their α-methylated counterparts methacrylonitrile and methyl methacrylate at the M06-2X(PCM)/TZVP level of theory has been performed. We want to understand the excellent exo-selectivities observed experimentally due the presence of this substituent. To this end, analysis of the reaction coordinate by means of activation strain model of chemical reactivity (ASM-distortion interaction model) including solvation effects and NBO second order perturbation energy have been carried out.