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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...

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Autores principales: Panda, Chakadola, Anny-Nzekwue, Onyinyechukwuka, Doyle, Lorna M., Gericke, Robert, McDonald, Aidan R.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
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.
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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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