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Mild and Chemoselective Carboxylic Acid Reduction Promoted by Borane Catalysis

Although considerable advances have been made in developing chemoselective transformations of ubiquitous carboxylic acid groups, many challenges still exist. For instance, their selective reduction is problematic if both more nucleophilic and more electrophilic groups are present in the starting mat...

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Autores principales: Lunic, Danijela, Sanosa, Nil, Funes‐Ardoiz, Ignacio, Teskey, Christopher J.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9825922/
https://www.ncbi.nlm.nih.gov/pubmed/36047716
http://dx.doi.org/10.1002/anie.202207647
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author Lunic, Danijela
Sanosa, Nil
Funes‐Ardoiz, Ignacio
Teskey, Christopher J.
author_facet Lunic, Danijela
Sanosa, Nil
Funes‐Ardoiz, Ignacio
Teskey, Christopher J.
author_sort Lunic, Danijela
collection PubMed
description Although considerable advances have been made in developing chemoselective transformations of ubiquitous carboxylic acid groups, many challenges still exist. For instance, their selective reduction is problematic if both more nucleophilic and more electrophilic groups are present in the starting material. Here, we address this problem with a simple and mild protocol using bench‐stable reagents at ambient temperatures. This platform is able to tolerate a diverse range of functionality, leaving ketones, esters, nitro‐groups, olefins, nitriles and amides untouched. A combination of experimental and computational mechanistic experiments demonstrate that this reaction proceeds via hidden borane catalysis with small quantities of in situ generated BH(3) playing a key role in the exquisite selectivity that is observed.
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spelling pubmed-98259222023-01-09 Mild and Chemoselective Carboxylic Acid Reduction Promoted by Borane Catalysis Lunic, Danijela Sanosa, Nil Funes‐Ardoiz, Ignacio Teskey, Christopher J. Angew Chem Int Ed Engl Communications Although considerable advances have been made in developing chemoselective transformations of ubiquitous carboxylic acid groups, many challenges still exist. For instance, their selective reduction is problematic if both more nucleophilic and more electrophilic groups are present in the starting material. Here, we address this problem with a simple and mild protocol using bench‐stable reagents at ambient temperatures. This platform is able to tolerate a diverse range of functionality, leaving ketones, esters, nitro‐groups, olefins, nitriles and amides untouched. A combination of experimental and computational mechanistic experiments demonstrate that this reaction proceeds via hidden borane catalysis with small quantities of in situ generated BH(3) playing a key role in the exquisite selectivity that is observed. John Wiley and Sons Inc. 2022-09-21 2022-10-24 /pmc/articles/PMC9825922/ /pubmed/36047716 http://dx.doi.org/10.1002/anie.202207647 Text en © 2022 The Authors. Angewandte Chemie International Edition 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 Communications
Lunic, Danijela
Sanosa, Nil
Funes‐Ardoiz, Ignacio
Teskey, Christopher J.
Mild and Chemoselective Carboxylic Acid Reduction Promoted by Borane Catalysis
title Mild and Chemoselective Carboxylic Acid Reduction Promoted by Borane Catalysis
title_full Mild and Chemoselective Carboxylic Acid Reduction Promoted by Borane Catalysis
title_fullStr Mild and Chemoselective Carboxylic Acid Reduction Promoted by Borane Catalysis
title_full_unstemmed Mild and Chemoselective Carboxylic Acid Reduction Promoted by Borane Catalysis
title_short Mild and Chemoselective Carboxylic Acid Reduction Promoted by Borane Catalysis
title_sort mild and chemoselective carboxylic acid reduction promoted by borane catalysis
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9825922/
https://www.ncbi.nlm.nih.gov/pubmed/36047716
http://dx.doi.org/10.1002/anie.202207647
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