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Synlett
DOI: 10.1055/a-2351-5090
DOI: 10.1055/a-2351-5090
synpacts
On the Existence and Relevance of Copper(III) Fluorides in Oxidative Trifluoromethylation
Financial support from the Centre National de la Recherche Scientifique (CNRS), the Université Toulouse III - Paul Sabatier, and the Agence Nationale de la Recherche (ANR-JCJC-20-CE07-0023, acronym Ni4Rf) is gratefully acknowledged. D.J-S thanks the ANR for postdoctoral funding.
Abstract
Numerous reports invoke CuIII–F intermediates engaging in oxidative cross-couplings mediated by low/mid-valent copper and formal sources of ‘F+’ oxidants. These elusive and typically instable CuIII fluorides have been rarely characterized or spectroscopically identified, making their existence and participation within catalytic cycles somehow questionable. We have authenticated a stable organocopper(III) fluoride that undergoes Csp–CF3 bond formation upon addition of silyl-capped alkynes following a 2 e– CuIII/CuI redox shuttle. This finding strongly supports the intermediacy of CuIII fluorides in C–C coupling. We review herein the state of the art about well-defined CuIII fluorides enabling cross-coupling reactions.
1 Introduction
2 Brief History of Coupling-Competent CuIII Fluorides
3 Design of an Isolable – yet Reactive – Organocopper(III) Fluoride
4 Alkyne Trifluoromethylation: Scope and Mechanism
5 Extension to Aryl–CF3 and C–Heteroatom Couplings
6 Summary and Outlook
Key words
trifluoromethylation - organocopper(III) compounds - CuIII fluorides - oxidative cross-coupling - 2 e– redox shuttlePublication History
Received: 22 May 2024
Accepted after revision: 24 June 2024
Accepted Manuscript online:
24 June 2024
Article published online:
16 July 2024
© 2024. Thieme. All rights reserved
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References and Notes
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Organofluorine compounds are valuable synthons in medicinal and agrochemistry or in material science:
For representative examples, see:
An alternative entry to III and related compounds IV–VI has been reported by employing AgF as a fluoride source and oxidant:
For two other examples of Ullmann–Goldberg fluorinations enabled by putative CuIII fluorides, see:
For reminiscent silver chemistry, see:
CuIII/F binary salts are known:
The combination of F– sources and an external oxidant has been already used with success to build high-valent nickel fluorides:
C–C couplings:
C–heteroatom couplings:
For recent reviews on the HLF reaction, see:
For some representative examples of halide exchange using AgF, see:
See ref. 38, 39, and: