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Effect of an ?-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 ?-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.

SUBMITTER: Larranaga O

PROVIDER: S-EPMC6333242 | biostudies-literature | 2019 Jan

REPOSITORIES: biostudies-literature

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

Larrañaga Olatz O de Cózar Abel A

ChemistryOpen 20190115 1

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 in ...[more]

PMID: 30652065

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