Cargando…
A third generation of radical fluorinating agents based on N-fluoro-N-arylsulfonamides
Radical fluorination has been known for a long time, but synthetic applications were severely limited by the hazardous nature of the first generation of reagents such as F(2) and the strongly electrophilic nature of the second generation of reagents such as N-fluorobenzenesulfonimide (NFSI) and Sele...
Autores principales: | , , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2018
|
Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6244228/ https://www.ncbi.nlm.nih.gov/pubmed/30459353 http://dx.doi.org/10.1038/s41467-018-07196-9 |
_version_ | 1783372045811187712 |
---|---|
author | Meyer, Daniel Jangra, Harish Walther, Fabian Zipse, Hendrik Renaud, Philippe |
author_facet | Meyer, Daniel Jangra, Harish Walther, Fabian Zipse, Hendrik Renaud, Philippe |
author_sort | Meyer, Daniel |
collection | PubMed |
description | Radical fluorination has been known for a long time, but synthetic applications were severely limited by the hazardous nature of the first generation of reagents such as F(2) and the strongly electrophilic nature of the second generation of reagents such as N-fluorobenzenesulfonimide (NFSI) and Selecfluor(®). Here, we report the preparation, use and properties of N-fluoro-N-arylsulfonamides (NFASs), a class of fluorinating reagents suitable for radical fluorination under mild conditions. Their N–F bond dissociation energies (BDE) are 30–45 kJ mol(−1) lower than the N–F BDE of the reagents of the second generation. This favors clean radical fluorination processes over undesired side reactions. The utility of NFASs is demonstrated by a metal-free radical hydrofluorination of alkenes including an efficient remote C–H fluorination via a 1,5-hydrogen atom transfer. NFASs have the potential to become the reagents of choice in many radical fluorination processes. |
format | Online Article Text |
id | pubmed-6244228 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2018 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-62442282018-11-21 A third generation of radical fluorinating agents based on N-fluoro-N-arylsulfonamides Meyer, Daniel Jangra, Harish Walther, Fabian Zipse, Hendrik Renaud, Philippe Nat Commun Article Radical fluorination has been known for a long time, but synthetic applications were severely limited by the hazardous nature of the first generation of reagents such as F(2) and the strongly electrophilic nature of the second generation of reagents such as N-fluorobenzenesulfonimide (NFSI) and Selecfluor(®). Here, we report the preparation, use and properties of N-fluoro-N-arylsulfonamides (NFASs), a class of fluorinating reagents suitable for radical fluorination under mild conditions. Their N–F bond dissociation energies (BDE) are 30–45 kJ mol(−1) lower than the N–F BDE of the reagents of the second generation. This favors clean radical fluorination processes over undesired side reactions. The utility of NFASs is demonstrated by a metal-free radical hydrofluorination of alkenes including an efficient remote C–H fluorination via a 1,5-hydrogen atom transfer. NFASs have the potential to become the reagents of choice in many radical fluorination processes. Nature Publishing Group UK 2018-11-20 /pmc/articles/PMC6244228/ /pubmed/30459353 http://dx.doi.org/10.1038/s41467-018-07196-9 Text en © The Author(s) 2018 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 Meyer, Daniel Jangra, Harish Walther, Fabian Zipse, Hendrik Renaud, Philippe A third generation of radical fluorinating agents based on N-fluoro-N-arylsulfonamides |
title | A third generation of radical fluorinating agents based on N-fluoro-N-arylsulfonamides |
title_full | A third generation of radical fluorinating agents based on N-fluoro-N-arylsulfonamides |
title_fullStr | A third generation of radical fluorinating agents based on N-fluoro-N-arylsulfonamides |
title_full_unstemmed | A third generation of radical fluorinating agents based on N-fluoro-N-arylsulfonamides |
title_short | A third generation of radical fluorinating agents based on N-fluoro-N-arylsulfonamides |
title_sort | third generation of radical fluorinating agents based on n-fluoro-n-arylsulfonamides |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6244228/ https://www.ncbi.nlm.nih.gov/pubmed/30459353 http://dx.doi.org/10.1038/s41467-018-07196-9 |
work_keys_str_mv | AT meyerdaniel athirdgenerationofradicalfluorinatingagentsbasedonnfluoronarylsulfonamides AT jangraharish athirdgenerationofradicalfluorinatingagentsbasedonnfluoronarylsulfonamides AT waltherfabian athirdgenerationofradicalfluorinatingagentsbasedonnfluoronarylsulfonamides AT zipsehendrik athirdgenerationofradicalfluorinatingagentsbasedonnfluoronarylsulfonamides AT renaudphilippe athirdgenerationofradicalfluorinatingagentsbasedonnfluoronarylsulfonamides AT meyerdaniel thirdgenerationofradicalfluorinatingagentsbasedonnfluoronarylsulfonamides AT jangraharish thirdgenerationofradicalfluorinatingagentsbasedonnfluoronarylsulfonamides AT waltherfabian thirdgenerationofradicalfluorinatingagentsbasedonnfluoronarylsulfonamides AT zipsehendrik thirdgenerationofradicalfluorinatingagentsbasedonnfluoronarylsulfonamides AT renaudphilippe thirdgenerationofradicalfluorinatingagentsbasedonnfluoronarylsulfonamides |