Evidence for a High-Valent Iron-Fluoride That Mediates Oxidative C(sp)-H Fluorination

Overview

Journal JACS Au

Publisher American Chemical Society

Specialty Chemistry

Date 2023 Apr 3

PMID 37006763

Authors

Chakadola Panda

Onyinyechukwuka Anny-Nzekwue

Lorna M Doyle

Robert Gericke

Aidan R McDonald

Affiliations

Soon will be listed here.

Abstract

[Fe(NCCH)(NTB)](OTf) (NTB = tris(2-benzimidazoylmethyl)amine, OTf = trifluoromethanesulfonate) was reacted with difluoro(phenyl)-λ-iodane (PhIF) 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(F) oxidant that performs hydrogen atom transfer followed by the formation of a dimeric μ-F-(Fe) 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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