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Evidence for a High-Valent Iron-Fluoride That Mediates Oxidative C(sp(3))-H Fluorination
[Image: see text] [Fe(II)(NCCH(3))(NTB)](OTf)(2) (NTB = tris(2-benzimidazoylmethyl)amine, OTf = trifluoromethanesulfonate) was reacted with difluoro(phenyl)-λ(3)-iodane (PhIF(2)) in the presence of a variety of saturated hydrocarbons, resulting in the oxidative fluorination of the hydrocarbons in mo...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10052241/ https://www.ncbi.nlm.nih.gov/pubmed/37006763 http://dx.doi.org/10.1021/jacsau.3c00021 |
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author | Panda, Chakadola Anny-Nzekwue, Onyinyechukwuka Doyle, Lorna M. Gericke, Robert McDonald, Aidan R. |
author_facet | Panda, Chakadola Anny-Nzekwue, Onyinyechukwuka Doyle, Lorna M. Gericke, Robert McDonald, Aidan R. |
author_sort | Panda, Chakadola |
collection | PubMed |
description | [Image: see text] [Fe(II)(NCCH(3))(NTB)](OTf)(2) (NTB = tris(2-benzimidazoylmethyl)amine, OTf = trifluoromethanesulfonate) was reacted with difluoro(phenyl)-λ(3)-iodane (PhIF(2)) in the presence of a variety of saturated hydrocarbons, resulting in the oxidative fluorination of the hydrocarbons in moderate-to-good yields. Kinetic and product analysis point towards a hydrogen atom transfer oxidation prior to fluorine radical rebound to form the fluorinated product. The combined evidence supports the formation of a formally Fe(IV)(F)(2) oxidant that performs hydrogen atom transfer followed by the formation of a dimeric μ-F–(Fe(III))(2) product that is a plausible fluorine atom transfer rebound reagent. This approach mimics the heme paradigm for hydrocarbon hydroxylation, opening up avenues for oxidative hydrocarbon halogenation. |
format | Online Article Text |
id | pubmed-10052241 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-100522412023-03-30 Evidence for a High-Valent Iron-Fluoride That Mediates Oxidative C(sp(3))-H Fluorination Panda, Chakadola Anny-Nzekwue, Onyinyechukwuka Doyle, Lorna M. Gericke, Robert McDonald, Aidan R. JACS Au [Image: see text] [Fe(II)(NCCH(3))(NTB)](OTf)(2) (NTB = tris(2-benzimidazoylmethyl)amine, OTf = trifluoromethanesulfonate) was reacted with difluoro(phenyl)-λ(3)-iodane (PhIF(2)) in the presence of a variety of saturated hydrocarbons, resulting in the oxidative fluorination of the hydrocarbons in moderate-to-good yields. Kinetic and product analysis point towards a hydrogen atom transfer oxidation prior to fluorine radical rebound to form the fluorinated product. The combined evidence supports the formation of a formally Fe(IV)(F)(2) oxidant that performs hydrogen atom transfer followed by the formation of a dimeric μ-F–(Fe(III))(2) product that is a plausible fluorine atom transfer rebound reagent. This approach mimics the heme paradigm for hydrocarbon hydroxylation, opening up avenues for oxidative hydrocarbon halogenation. American Chemical Society 2023-03-03 /pmc/articles/PMC10052241/ /pubmed/37006763 http://dx.doi.org/10.1021/jacsau.3c00021 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Panda, Chakadola Anny-Nzekwue, Onyinyechukwuka Doyle, Lorna M. Gericke, Robert McDonald, Aidan R. Evidence for a High-Valent Iron-Fluoride That Mediates Oxidative C(sp(3))-H Fluorination |
title | Evidence for a High-Valent
Iron-Fluoride That Mediates
Oxidative C(sp(3))-H Fluorination |
title_full | Evidence for a High-Valent
Iron-Fluoride That Mediates
Oxidative C(sp(3))-H Fluorination |
title_fullStr | Evidence for a High-Valent
Iron-Fluoride That Mediates
Oxidative C(sp(3))-H Fluorination |
title_full_unstemmed | Evidence for a High-Valent
Iron-Fluoride That Mediates
Oxidative C(sp(3))-H Fluorination |
title_short | Evidence for a High-Valent
Iron-Fluoride That Mediates
Oxidative C(sp(3))-H Fluorination |
title_sort | evidence for a high-valent
iron-fluoride that mediates
oxidative c(sp(3))-h fluorination |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10052241/ https://www.ncbi.nlm.nih.gov/pubmed/37006763 http://dx.doi.org/10.1021/jacsau.3c00021 |
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