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Mechanism of Cu-Catalyzed Iododeboronation: A Description of Ligand-Enabled Transmetalation, Disproportionation, and Turnover in Cu-Mediated Oxidative Coupling Reactions
[Image: see text] We report a combined experimental and computational study of the mechanism of the Cu-catalyzed arylboronic acid iododeboronation reaction. A combination of structural and density functional theory (DFT) analyses has allowed determination of the identity of the reaction precatalyst...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10442916/ https://www.ncbi.nlm.nih.gov/pubmed/37614524 http://dx.doi.org/10.1021/acscatal.3c02839 |
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author | Andrews, Matthew J. Carpentier, Ambre Slawin, Alexandra M. Z. Cordes, David B. Macgregor, Stuart A. Watson, Allan J. B. |
author_facet | Andrews, Matthew J. Carpentier, Ambre Slawin, Alexandra M. Z. Cordes, David B. Macgregor, Stuart A. Watson, Allan J. B. |
author_sort | Andrews, Matthew J. |
collection | PubMed |
description | [Image: see text] We report a combined experimental and computational study of the mechanism of the Cu-catalyzed arylboronic acid iododeboronation reaction. A combination of structural and density functional theory (DFT) analyses has allowed determination of the identity of the reaction precatalyst with insight into each step of the catalytic cycle. Key findings include a rationale for ligand (phen) stoichiometry related to key turnover events—the ligand facilitates transmetalation via H-bonding to an organoboron boronate generated in situ and phen loss/gain is integral to the key oxidative events. These data provide a framework for understanding ligand effects on these key mechanistic processes, which underpin several classes of Cu-mediated oxidative coupling reactions. |
format | Online Article Text |
id | pubmed-10442916 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-104429162023-08-23 Mechanism of Cu-Catalyzed Iododeboronation: A Description of Ligand-Enabled Transmetalation, Disproportionation, and Turnover in Cu-Mediated Oxidative Coupling Reactions Andrews, Matthew J. Carpentier, Ambre Slawin, Alexandra M. Z. Cordes, David B. Macgregor, Stuart A. Watson, Allan J. B. ACS Catal [Image: see text] We report a combined experimental and computational study of the mechanism of the Cu-catalyzed arylboronic acid iododeboronation reaction. A combination of structural and density functional theory (DFT) analyses has allowed determination of the identity of the reaction precatalyst with insight into each step of the catalytic cycle. Key findings include a rationale for ligand (phen) stoichiometry related to key turnover events—the ligand facilitates transmetalation via H-bonding to an organoboron boronate generated in situ and phen loss/gain is integral to the key oxidative events. These data provide a framework for understanding ligand effects on these key mechanistic processes, which underpin several classes of Cu-mediated oxidative coupling reactions. American Chemical Society 2023-08-07 /pmc/articles/PMC10442916/ /pubmed/37614524 http://dx.doi.org/10.1021/acscatal.3c02839 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Andrews, Matthew J. Carpentier, Ambre Slawin, Alexandra M. Z. Cordes, David B. Macgregor, Stuart A. Watson, Allan J. B. Mechanism of Cu-Catalyzed Iododeboronation: A Description of Ligand-Enabled Transmetalation, Disproportionation, and Turnover in Cu-Mediated Oxidative Coupling Reactions |
title | Mechanism of Cu-Catalyzed
Iododeboronation: A Description
of Ligand-Enabled Transmetalation, Disproportionation, and Turnover
in Cu-Mediated Oxidative Coupling Reactions |
title_full | Mechanism of Cu-Catalyzed
Iododeboronation: A Description
of Ligand-Enabled Transmetalation, Disproportionation, and Turnover
in Cu-Mediated Oxidative Coupling Reactions |
title_fullStr | Mechanism of Cu-Catalyzed
Iododeboronation: A Description
of Ligand-Enabled Transmetalation, Disproportionation, and Turnover
in Cu-Mediated Oxidative Coupling Reactions |
title_full_unstemmed | Mechanism of Cu-Catalyzed
Iododeboronation: A Description
of Ligand-Enabled Transmetalation, Disproportionation, and Turnover
in Cu-Mediated Oxidative Coupling Reactions |
title_short | Mechanism of Cu-Catalyzed
Iododeboronation: A Description
of Ligand-Enabled Transmetalation, Disproportionation, and Turnover
in Cu-Mediated Oxidative Coupling Reactions |
title_sort | mechanism of cu-catalyzed
iododeboronation: a description
of ligand-enabled transmetalation, disproportionation, and turnover
in cu-mediated oxidative coupling reactions |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10442916/ https://www.ncbi.nlm.nih.gov/pubmed/37614524 http://dx.doi.org/10.1021/acscatal.3c02839 |
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