Cargando…
Diastereoselectivity on Intramolecular Alder‐ene Reaction of 1,6‐Dienes
A detailed computational study of the intramolecular Alder‐ene reaction of different 1,6‐dienes at M06‐2X(PCM)/TZ2P level of theory has been performed. We want to understand the influence of enophile‐geminal substitution pattern in the cis : trans selectivity of the cyclization process. Our analysis...
Autor principal: | |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2022
|
Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10087545/ https://www.ncbi.nlm.nih.gov/pubmed/35942565 http://dx.doi.org/10.1002/cphc.202200377 |
_version_ | 1785022372499161088 |
---|---|
author | de Cózar, Abel |
author_facet | de Cózar, Abel |
author_sort | de Cózar, Abel |
collection | PubMed |
description | A detailed computational study of the intramolecular Alder‐ene reaction of different 1,6‐dienes at M06‐2X(PCM)/TZ2P level of theory has been performed. We want to understand the influence of enophile‐geminal substitution pattern in the cis : trans selectivity of the cyclization process. Our analysis of the reaction coordinate by means of activation strain model of chemical reactivity (ASM‐distortion interaction model) reveals that the cis‐selectivity observed for unactivated reagents is related with high stabilizing orbital interaction and lower strain energy, consequence of an early transition structure. On the other hand, the presence of activating groups increases the asynchronicity of the transition structures and reduces the activation barrier due to more stabilizing orbital and electrostatic interactions, favoring trans‐selectivity. |
format | Online Article Text |
id | pubmed-10087545 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-100875452023-04-12 Diastereoselectivity on Intramolecular Alder‐ene Reaction of 1,6‐Dienes de Cózar, Abel Chemphyschem Research Articles A detailed computational study of the intramolecular Alder‐ene reaction of different 1,6‐dienes at M06‐2X(PCM)/TZ2P level of theory has been performed. We want to understand the influence of enophile‐geminal substitution pattern in the cis : trans selectivity of the cyclization process. Our analysis of the reaction coordinate by means of activation strain model of chemical reactivity (ASM‐distortion interaction model) reveals that the cis‐selectivity observed for unactivated reagents is related with high stabilizing orbital interaction and lower strain energy, consequence of an early transition structure. On the other hand, the presence of activating groups increases the asynchronicity of the transition structures and reduces the activation barrier due to more stabilizing orbital and electrostatic interactions, favoring trans‐selectivity. John Wiley and Sons Inc. 2022-09-02 2022-12-05 /pmc/articles/PMC10087545/ /pubmed/35942565 http://dx.doi.org/10.1002/cphc.202200377 Text en © 2022 The Authors. ChemPhysChem published by Wiley-VCH GmbH https://creativecommons.org/licenses/by-nc-nd/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ (https://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 | Research Articles de Cózar, Abel Diastereoselectivity on Intramolecular Alder‐ene Reaction of 1,6‐Dienes |
title | Diastereoselectivity on Intramolecular Alder‐ene Reaction of 1,6‐Dienes |
title_full | Diastereoselectivity on Intramolecular Alder‐ene Reaction of 1,6‐Dienes |
title_fullStr | Diastereoselectivity on Intramolecular Alder‐ene Reaction of 1,6‐Dienes |
title_full_unstemmed | Diastereoselectivity on Intramolecular Alder‐ene Reaction of 1,6‐Dienes |
title_short | Diastereoselectivity on Intramolecular Alder‐ene Reaction of 1,6‐Dienes |
title_sort | diastereoselectivity on intramolecular alder‐ene reaction of 1,6‐dienes |
topic | Research Articles |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10087545/ https://www.ncbi.nlm.nih.gov/pubmed/35942565 http://dx.doi.org/10.1002/cphc.202200377 |
work_keys_str_mv | AT decozarabel diastereoselectivityonintramolecularalderenereactionof16dienes |