Zirconium-mediated Carbon-fluorine Bond Functionalisation Through Cyclohexyne "umpolung"

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Date 2025 Jan 27

PMID 39867955

Authors

Sara Bonfante

Theo F N Tanner

Christian Lorber

Jason M Lynam

Antoine Simonneau

John M Slattery

Affiliations

Soon will be listed here.

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 PMe were observed when pentafluoropyridine was the substrate.

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