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Oxidative Addition of Water, Alcohols, and Amines in Palladium Catalysis
The homolytic cleavage of O−H and N−H or weak C−H bonds is a key elementary step in redox catalysis, but is thought to be unfeasible for palladium. In stark contrast, reported here is the room temperature and reversible oxidative addition of water, isopropanol, hexafluoroisopropanol, phenol, and ani...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7692900/ https://www.ncbi.nlm.nih.gov/pubmed/32745317 http://dx.doi.org/10.1002/anie.202008350 |
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author | Grünwald, Annette Heinemann, Frank W. Munz, Dominik |
author_facet | Grünwald, Annette Heinemann, Frank W. Munz, Dominik |
author_sort | Grünwald, Annette |
collection | PubMed |
description | The homolytic cleavage of O−H and N−H or weak C−H bonds is a key elementary step in redox catalysis, but is thought to be unfeasible for palladium. In stark contrast, reported here is the room temperature and reversible oxidative addition of water, isopropanol, hexafluoroisopropanol, phenol, and aniline to a palladium(0) complex with a cyclic (alkyl)(amino)carbene (CAAC) and a labile pyridino ligand, as is also the case in popular N‐heterocyclic carbene (NHC) palladium(II) precatalysts. The oxidative addition of protic solvents or adventitious water switches the chemoselectivity in catalysis with alkynes through activation of the terminal C−H bond. Most salient, the homolytic activation of alcohols and amines allows atom‐efficient, additive‐free cross‐coupling and transfer hydrogenation under mild reaction conditions with usually unreactive, yet desirable reagents, including esters and bis(pinacolato)diboron. |
format | Online Article Text |
id | pubmed-7692900 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-76929002020-12-08 Oxidative Addition of Water, Alcohols, and Amines in Palladium Catalysis Grünwald, Annette Heinemann, Frank W. Munz, Dominik Angew Chem Int Ed Engl Research Articles The homolytic cleavage of O−H and N−H or weak C−H bonds is a key elementary step in redox catalysis, but is thought to be unfeasible for palladium. In stark contrast, reported here is the room temperature and reversible oxidative addition of water, isopropanol, hexafluoroisopropanol, phenol, and aniline to a palladium(0) complex with a cyclic (alkyl)(amino)carbene (CAAC) and a labile pyridino ligand, as is also the case in popular N‐heterocyclic carbene (NHC) palladium(II) precatalysts. The oxidative addition of protic solvents or adventitious water switches the chemoselectivity in catalysis with alkynes through activation of the terminal C−H bond. Most salient, the homolytic activation of alcohols and amines allows atom‐efficient, additive‐free cross‐coupling and transfer hydrogenation under mild reaction conditions with usually unreactive, yet desirable reagents, including esters and bis(pinacolato)diboron. John Wiley and Sons Inc. 2020-09-21 2020-11-16 /pmc/articles/PMC7692900/ /pubmed/32745317 http://dx.doi.org/10.1002/anie.202008350 Text en © 2020 The Authors. Published by Wiley-VCH GmbH This is an open access article under the terms of the http://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 Grünwald, Annette Heinemann, Frank W. Munz, Dominik Oxidative Addition of Water, Alcohols, and Amines in Palladium Catalysis |
title | Oxidative Addition of Water, Alcohols, and Amines in Palladium Catalysis |
title_full | Oxidative Addition of Water, Alcohols, and Amines in Palladium Catalysis |
title_fullStr | Oxidative Addition of Water, Alcohols, and Amines in Palladium Catalysis |
title_full_unstemmed | Oxidative Addition of Water, Alcohols, and Amines in Palladium Catalysis |
title_short | Oxidative Addition of Water, Alcohols, and Amines in Palladium Catalysis |
title_sort | oxidative addition of water, alcohols, and amines in palladium catalysis |
topic | Research Articles |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7692900/ https://www.ncbi.nlm.nih.gov/pubmed/32745317 http://dx.doi.org/10.1002/anie.202008350 |
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