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

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‐selectivi...

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Detalles Bibliográficos
Autores principales: Larrañaga, Olatz, de Cózar, Abel
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2019
Materias:
Full Papers
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6333242/
https://www.ncbi.nlm.nih.gov/pubmed/30652065
http://dx.doi.org/10.1002/open.201800237
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author Larrañaga, Olatz
de Cózar, Abel
author_facet Larrañaga, Olatz
de Cózar, Abel
author_sort Larrañaga, Olatz
collection PubMed
description 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.
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spelling pubmed-63332422019-01-16 Effect of an α‐Methyl Substituent on the Dienophile on Diels‐Alder endo:exo Selectivity Larrañaga, Olatz de Cózar, Abel ChemistryOpen Full Papers 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. John Wiley and Sons Inc. 2019-01-15 /pmc/articles/PMC6333242/ /pubmed/30652065 http://dx.doi.org/10.1002/open.201800237 Text en © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.
spellingShingle Full Papers
Larrañaga, Olatz
de Cózar, Abel
Effect of an α‐Methyl Substituent on the Dienophile on Diels‐Alder endo:exo Selectivity
title Effect of an α‐Methyl Substituent on the Dienophile on Diels‐Alder endo:exo Selectivity
title_full Effect of an α‐Methyl Substituent on the Dienophile on Diels‐Alder endo:exo Selectivity
title_fullStr Effect of an α‐Methyl Substituent on the Dienophile on Diels‐Alder endo:exo Selectivity
title_full_unstemmed Effect of an α‐Methyl Substituent on the Dienophile on Diels‐Alder endo:exo Selectivity
title_short Effect of an α‐Methyl Substituent on the Dienophile on Diels‐Alder endo:exo Selectivity
title_sort effect of an α‐methyl substituent on the dienophile on diels‐alder endo:exo selectivity
topic Full Papers
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6333242/
https://www.ncbi.nlm.nih.gov/pubmed/30652065
http://dx.doi.org/10.1002/open.201800237
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