Open AccessEffect of an α‐Methyl Substituent on the Dienophile on Diels‐Alder endo : exo Selectivity
Author(s) -
Larrañaga Olatz,
de Cózar Abel
Publication year - 2019
Publication title -
chemistryopen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.644
H-Index - 29
ISSN - 2191-1363
DOI - 10.1002/open.201800237
Subject(s) - substituent , methacrylonitrile , cyclopentadiene , acrylonitrile , chemistry , selectivity , diels–alder reaction , computational chemistry , solvation , isoprene , methyl methacrylate , natural bond orbital , organic chemistry , density functional theory , copolymer , solvent , polymer , catalysis
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.