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Updated: May 30, 2025

Author Spotlight: Functionalizing Metal-Organic Frameworks: Advancements, Challenges, and the Power of Post-Synthetic Ligand Exchange
Published on: June 23, 2023
Zirconium-mediated carbon-fluorine bond functionalisation through cyclohexyne "umpolung"
Sara Bonfante1,2, Theo F N Tanner2, Christian Lorber1
1LCC-CNRS, Université de Toulouse, CNRS UPS205route de Narbonne BP44099 F-31077 Toulouse cedex 4 France.
Abstract:
Polarity reversal, or "umpolung", is a widely acknowledged strategy to allow organic functional groups amenable to react in alternative ways to the usual preference set by their electronic features. In this article, we demonstrate that cyclohexyne umpolung, realized through complexation to zirconocene, makes the small strained cycloalkyne amenable to C-F bond functionalisation. Such strong bond activation chemistry is unprecedented in "free" aryne and strained alkyne chemistry. Our study also reveals that the reactivity of the Zr-cyclohexyne complex is highly sensitive to the degree of fluorination of the heteroarene. In addition, parasitic reactions of the ancillary ligand PMe3 were observed when pentafluoropyridine was the substrate.
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