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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...

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Autores principales: Grünwald, Annette, Heinemann, Frank W., Munz, Dominik
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2020
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.
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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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