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Metal-free disproportionation of formic acid mediated by organoboranes

In the presence of dialkylboranes, formic acid can be converted to formaldehyde and methanol derivatives without the need for an external reductant. This reactivity, in which formates serve as the sole carbon and hydride sources, represents the first example of the disproportionation of formate anio...

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Autores principales: Chauvier, Clément, Thuéry, Pierre, Cantat, Thibault
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2016
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6021958/
https://www.ncbi.nlm.nih.gov/pubmed/30034706
http://dx.doi.org/10.1039/c6sc01410k
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author Chauvier, Clément
Thuéry, Pierre
Cantat, Thibault
author_facet Chauvier, Clément
Thuéry, Pierre
Cantat, Thibault
author_sort Chauvier, Clément
collection PubMed
description In the presence of dialkylboranes, formic acid can be converted to formaldehyde and methanol derivatives without the need for an external reductant. This reactivity, in which formates serve as the sole carbon and hydride sources, represents the first example of the disproportionation of formate anions under metal-free conditions. Capitalizing on both experimental and computational (DFT) mechanistic considerations, the role of transient borohydride is highlighted in the reduction of formates and this reactivity was further exemplified in the methylation of TMP (2,2,6,6-tetramethylpiperidine) and in the transfer hydroboration reactions for the reduction of aldehydes.
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spelling pubmed-60219582018-07-20 Metal-free disproportionation of formic acid mediated by organoboranes Chauvier, Clément Thuéry, Pierre Cantat, Thibault Chem Sci Chemistry In the presence of dialkylboranes, formic acid can be converted to formaldehyde and methanol derivatives without the need for an external reductant. This reactivity, in which formates serve as the sole carbon and hydride sources, represents the first example of the disproportionation of formate anions under metal-free conditions. Capitalizing on both experimental and computational (DFT) mechanistic considerations, the role of transient borohydride is highlighted in the reduction of formates and this reactivity was further exemplified in the methylation of TMP (2,2,6,6-tetramethylpiperidine) and in the transfer hydroboration reactions for the reduction of aldehydes. Royal Society of Chemistry 2016-09-01 2016-05-19 /pmc/articles/PMC6021958/ /pubmed/30034706 http://dx.doi.org/10.1039/c6sc01410k Text en This journal is © The Royal Society of Chemistry 2016 https://creativecommons.org/licenses/by-nc/3.0/This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0)
spellingShingle Chemistry
Chauvier, Clément
Thuéry, Pierre
Cantat, Thibault
Metal-free disproportionation of formic acid mediated by organoboranes
title Metal-free disproportionation of formic acid mediated by organoboranes
title_full Metal-free disproportionation of formic acid mediated by organoboranes
title_fullStr Metal-free disproportionation of formic acid mediated by organoboranes
title_full_unstemmed Metal-free disproportionation of formic acid mediated by organoboranes
title_short Metal-free disproportionation of formic acid mediated by organoboranes
title_sort metal-free disproportionation of formic acid mediated by organoboranes
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6021958/
https://www.ncbi.nlm.nih.gov/pubmed/30034706
http://dx.doi.org/10.1039/c6sc01410k
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