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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...

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Autores principales: Cabrera‐Trujillo, Jorge Juan, Fernández, Israel
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2021
Materias:
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.
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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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