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Factors Controlling the Aluminum(I)‐meta‐Selective C−H Activation in Arenes
The so far poorly understood factors controlling the complete meta‐selectivity observed in the C−H activation reactions of alkylarenes promoted by aluminyl anions have been explored in detail by means of Density Functional Theory calculations. To this end, a combination of state‐of‐the‐art computati...
Autores principales: | , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2021
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8457071/ https://www.ncbi.nlm.nih.gov/pubmed/34184800 http://dx.doi.org/10.1002/chem.202101944 |
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author | Cabrera‐Trujillo, Jorge Juan Fernández, Israel |
author_facet | Cabrera‐Trujillo, Jorge Juan Fernández, Israel |
author_sort | Cabrera‐Trujillo, Jorge Juan |
collection | PubMed |
description | The so far poorly understood factors controlling the complete meta‐selectivity observed in the C−H activation reactions of alkylarenes promoted by aluminyl anions have been explored in detail by means of Density Functional Theory calculations. To this end, a combination of state‐of‐the‐art computational methods, namely the activation strain model of reactivity and energy decomposition analysis, has been applied to quantitatively unveil the origin of the selectivity of the transformation as well as the influence of the associated potassium cation. It is found that the selectivity takes place during the initial nucleophilic addition step where the key LP(Al)→π*(C=C) molecular orbital interaction is more stabilizing for the meta‐pathway, which results in a stronger interaction between the reactants along the entire transformation. |
format | Online Article Text |
id | pubmed-8457071 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-84570712021-09-27 Factors Controlling the Aluminum(I)‐meta‐Selective C−H Activation in Arenes Cabrera‐Trujillo, Jorge Juan Fernández, Israel Chemistry Full Papers The so far poorly understood factors controlling the complete meta‐selectivity observed in the C−H activation reactions of alkylarenes promoted by aluminyl anions have been explored in detail by means of Density Functional Theory calculations. To this end, a combination of state‐of‐the‐art computational methods, namely the activation strain model of reactivity and energy decomposition analysis, has been applied to quantitatively unveil the origin of the selectivity of the transformation as well as the influence of the associated potassium cation. It is found that the selectivity takes place during the initial nucleophilic addition step where the key LP(Al)→π*(C=C) molecular orbital interaction is more stabilizing for the meta‐pathway, which results in a stronger interaction between the reactants along the entire transformation. John Wiley and Sons Inc. 2021-07-22 2021-08-25 /pmc/articles/PMC8457071/ /pubmed/34184800 http://dx.doi.org/10.1002/chem.202101944 Text en © 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Full Papers Cabrera‐Trujillo, Jorge Juan Fernández, Israel Factors Controlling the Aluminum(I)‐meta‐Selective C−H Activation in Arenes |
title | Factors Controlling the Aluminum(I)‐meta‐Selective C−H Activation in Arenes |
title_full | Factors Controlling the Aluminum(I)‐meta‐Selective C−H Activation in Arenes |
title_fullStr | Factors Controlling the Aluminum(I)‐meta‐Selective C−H Activation in Arenes |
title_full_unstemmed | Factors Controlling the Aluminum(I)‐meta‐Selective C−H Activation in Arenes |
title_short | Factors Controlling the Aluminum(I)‐meta‐Selective C−H Activation in Arenes |
title_sort | factors controlling the aluminum(i)‐meta‐selective c−h activation in arenes |
topic | Full Papers |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8457071/ https://www.ncbi.nlm.nih.gov/pubmed/34184800 http://dx.doi.org/10.1002/chem.202101944 |
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