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Encapsulation Enhances the Catalytic Activity of C‐N Coupling: Reaction Mechanism of a Cu(I)/Calix[8]arene Supramolecular Catalyst
Development of C−N coupling methodologies based on Earth‐abundant metals is a promising strategy in homogeneous catalysis for sustainable processes. However, such systems suffer from deactivation and low catalytic activity. We here report that encapsulation of Cu(I) within the phenanthroyl‐containin...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9804476/ https://www.ncbi.nlm.nih.gov/pubmed/36605358 http://dx.doi.org/10.1002/cctc.202200662 |
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author | Talmazan, Radu A. Refugio Monroy, J. del Río‐Portilla, Federico Castillo, Ivan Podewitz, Maren |
author_facet | Talmazan, Radu A. Refugio Monroy, J. del Río‐Portilla, Federico Castillo, Ivan Podewitz, Maren |
author_sort | Talmazan, Radu A. |
collection | PubMed |
description | Development of C−N coupling methodologies based on Earth‐abundant metals is a promising strategy in homogeneous catalysis for sustainable processes. However, such systems suffer from deactivation and low catalytic activity. We here report that encapsulation of Cu(I) within the phenanthroyl‐containing calix[8]arene derivative 1,5‐(2,9‐dimethyl‐1,10‐phenanthroyl)‐2,3,4,6,7,8‐hexamethyl‐p‐tert‐butylcalix[8]arene (C(8)PhenMe(6) ) significantly enhances C−N coupling activity up to 92 % yield in the reaction of aryl halides and aryl amines, with low catalyst loadings (2.5 % mol). A tailored multiscale computational protocol based on Molecular Dynamics simulations and DFT investigations revealed an oxidative addition/reductive elimination process of the supramolecular catalyst [Cu(C(8)PhenMe(6))I]. The computational investigations uncovered the origins of the enhanced catalytic activity over its molecular analogues: Catalyst deactivation through dimerization is prevented, and product release facilitated. Capturing the dynamic profile of the macrocycle and the impact of non‐covalent interactions on reactivity allows for the rationalization of the behavior of the flexible supramolecular catalysts employed. |
format | Online Article Text |
id | pubmed-9804476 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-98044762023-01-03 Encapsulation Enhances the Catalytic Activity of C‐N Coupling: Reaction Mechanism of a Cu(I)/Calix[8]arene Supramolecular Catalyst Talmazan, Radu A. Refugio Monroy, J. del Río‐Portilla, Federico Castillo, Ivan Podewitz, Maren ChemCatChem Research Articles Development of C−N coupling methodologies based on Earth‐abundant metals is a promising strategy in homogeneous catalysis for sustainable processes. However, such systems suffer from deactivation and low catalytic activity. We here report that encapsulation of Cu(I) within the phenanthroyl‐containing calix[8]arene derivative 1,5‐(2,9‐dimethyl‐1,10‐phenanthroyl)‐2,3,4,6,7,8‐hexamethyl‐p‐tert‐butylcalix[8]arene (C(8)PhenMe(6) ) significantly enhances C−N coupling activity up to 92 % yield in the reaction of aryl halides and aryl amines, with low catalyst loadings (2.5 % mol). A tailored multiscale computational protocol based on Molecular Dynamics simulations and DFT investigations revealed an oxidative addition/reductive elimination process of the supramolecular catalyst [Cu(C(8)PhenMe(6))I]. The computational investigations uncovered the origins of the enhanced catalytic activity over its molecular analogues: Catalyst deactivation through dimerization is prevented, and product release facilitated. Capturing the dynamic profile of the macrocycle and the impact of non‐covalent interactions on reactivity allows for the rationalization of the behavior of the flexible supramolecular catalysts employed. John Wiley and Sons Inc. 2022-09-01 2022-10-21 /pmc/articles/PMC9804476/ /pubmed/36605358 http://dx.doi.org/10.1002/cctc.202200662 Text en © 2022 The Authors. ChemCatChem 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 | Research Articles Talmazan, Radu A. Refugio Monroy, J. del Río‐Portilla, Federico Castillo, Ivan Podewitz, Maren Encapsulation Enhances the Catalytic Activity of C‐N Coupling: Reaction Mechanism of a Cu(I)/Calix[8]arene Supramolecular Catalyst |
title | Encapsulation Enhances the Catalytic Activity of C‐N Coupling: Reaction Mechanism of a Cu(I)/Calix[8]arene Supramolecular Catalyst |
title_full | Encapsulation Enhances the Catalytic Activity of C‐N Coupling: Reaction Mechanism of a Cu(I)/Calix[8]arene Supramolecular Catalyst |
title_fullStr | Encapsulation Enhances the Catalytic Activity of C‐N Coupling: Reaction Mechanism of a Cu(I)/Calix[8]arene Supramolecular Catalyst |
title_full_unstemmed | Encapsulation Enhances the Catalytic Activity of C‐N Coupling: Reaction Mechanism of a Cu(I)/Calix[8]arene Supramolecular Catalyst |
title_short | Encapsulation Enhances the Catalytic Activity of C‐N Coupling: Reaction Mechanism of a Cu(I)/Calix[8]arene Supramolecular Catalyst |
title_sort | encapsulation enhances the catalytic activity of c‐n coupling: reaction mechanism of a cu(i)/calix[8]arene supramolecular catalyst |
topic | Research Articles |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9804476/ https://www.ncbi.nlm.nih.gov/pubmed/36605358 http://dx.doi.org/10.1002/cctc.202200662 |
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