Ligand-Enabled Oxidative Fluorination of Gold(I) and Light-Induced Aryl–F Coupling at Gold(III) - Université de Pau et des Pays de l'Adour
Journal Articles Journal of the American Chemical Society Year : 2024

Ligand-Enabled Oxidative Fluorination of Gold(I) and Light-Induced Aryl–F Coupling at Gold(III)

Abstract

MeDalphos Au(I) complexes featuring aryl, alkynyl, and alkyl groups readily react with electrophilic fluorinating reagents such as N-fluorobenzenesulfonimide and Selectfluor. The ensuing [(MeDalphos)Au(R)F]+ complexes have been isolated and characterized by multinuclear NMR spectroscopy as well as X-ray diffraction. They adopt a square-planar contra-thermodynamic structure, with F trans to N. DFT/IBO calculations show that the N lone pair of MeDalphos assists and directs the transfer of F+ to gold. The [(MeDalphos)Au(Ar)F]+ (Ar = Mes, 2,6-F2Ph) complexes smoothly engage in C-C cross-coupling with PhCCSiMe3 and Me3SiCN, providing direct evidence for the oxidative fluorination/transmetalation/reductive elimination sequence proposed for F+-promoted gold-catalyzed transformations. Moreover, direct reductive elimination to forge a C-F bond at Au(III) was explored and substantiated. Thermal means proved unsuccessful, leading mostly to decomposition, but irradiation with UV-visible light enabled efficient promotion of aryl-F coupling (up to 90% yield). The light-induced reductive elimination proceeds under mild conditions; it works even with the electron-deprived 2,6-difluorophenyl group, and it is not limited to the contra-thermodynamic form of the aryl Au(III) fluoride complexes.
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hal-04570217 , version 1 (16-07-2024)

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David Vesseur, Shuo Li, Sonia Mallet-Ladeira, Karinne Miqueu, Didier Bourissou. Ligand-Enabled Oxidative Fluorination of Gold(I) and Light-Induced Aryl–F Coupling at Gold(III). Journal of the American Chemical Society, 2024, 146 (16), pp.11352-11363. ⟨10.1021/jacs.4c00913⟩. ⟨hal-04570217⟩
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