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Rational development of catalytic Au(I)/Au(III) arylation involving mild oxidative addition of aryl halides
The reluctance of gold to achieve oxidative addition reaction is considered as an intrinsic limitation for the development of gold-catalyzed cross-coupling reactions with simple and ubiquitous aryl halide electrophiles. Here, we report the rational construction of a Au(I)/Au(III) catalytic cycle inv...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2017
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5603523/ https://www.ncbi.nlm.nih.gov/pubmed/28924193 http://dx.doi.org/10.1038/s41467-017-00672-8 |
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author | Zeineddine, Abdallah Estévez, Laura Mallet-Ladeira, Sonia Miqueu, Karinne Amgoune, Abderrahmane Bourissou, Didier |
author_facet | Zeineddine, Abdallah Estévez, Laura Mallet-Ladeira, Sonia Miqueu, Karinne Amgoune, Abderrahmane Bourissou, Didier |
author_sort | Zeineddine, Abdallah |
collection | PubMed |
description | The reluctance of gold to achieve oxidative addition reaction is considered as an intrinsic limitation for the development of gold-catalyzed cross-coupling reactions with simple and ubiquitous aryl halide electrophiles. Here, we report the rational construction of a Au(I)/Au(III) catalytic cycle involving a sequence of Csp(2)–X oxidative addition, Csp(2)–H auration and reductive elimination, allowing a gold-catalyzed direct arylation of arenes with aryl halides. Key to this discovery is the use of Me-Dalphos, a simple ancillary (P,N) ligand, that allows the bottleneck oxidative addition of aryl iodides and bromides to readily proceed under mild conditions. The hemilabile character of the amino group plays a crucial role in this transformation, as substantiated by density functional theory calculations. |
format | Online Article Text |
id | pubmed-5603523 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2017 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-56035232017-09-22 Rational development of catalytic Au(I)/Au(III) arylation involving mild oxidative addition of aryl halides Zeineddine, Abdallah Estévez, Laura Mallet-Ladeira, Sonia Miqueu, Karinne Amgoune, Abderrahmane Bourissou, Didier Nat Commun Article The reluctance of gold to achieve oxidative addition reaction is considered as an intrinsic limitation for the development of gold-catalyzed cross-coupling reactions with simple and ubiquitous aryl halide electrophiles. Here, we report the rational construction of a Au(I)/Au(III) catalytic cycle involving a sequence of Csp(2)–X oxidative addition, Csp(2)–H auration and reductive elimination, allowing a gold-catalyzed direct arylation of arenes with aryl halides. Key to this discovery is the use of Me-Dalphos, a simple ancillary (P,N) ligand, that allows the bottleneck oxidative addition of aryl iodides and bromides to readily proceed under mild conditions. The hemilabile character of the amino group plays a crucial role in this transformation, as substantiated by density functional theory calculations. Nature Publishing Group UK 2017-09-18 /pmc/articles/PMC5603523/ /pubmed/28924193 http://dx.doi.org/10.1038/s41467-017-00672-8 Text en © The Author(s) 2017 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/. |
spellingShingle | Article Zeineddine, Abdallah Estévez, Laura Mallet-Ladeira, Sonia Miqueu, Karinne Amgoune, Abderrahmane Bourissou, Didier Rational development of catalytic Au(I)/Au(III) arylation involving mild oxidative addition of aryl halides |
title | Rational development of catalytic Au(I)/Au(III) arylation involving mild oxidative addition of aryl halides |
title_full | Rational development of catalytic Au(I)/Au(III) arylation involving mild oxidative addition of aryl halides |
title_fullStr | Rational development of catalytic Au(I)/Au(III) arylation involving mild oxidative addition of aryl halides |
title_full_unstemmed | Rational development of catalytic Au(I)/Au(III) arylation involving mild oxidative addition of aryl halides |
title_short | Rational development of catalytic Au(I)/Au(III) arylation involving mild oxidative addition of aryl halides |
title_sort | rational development of catalytic au(i)/au(iii) arylation involving mild oxidative addition of aryl halides |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5603523/ https://www.ncbi.nlm.nih.gov/pubmed/28924193 http://dx.doi.org/10.1038/s41467-017-00672-8 |
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