Zirconium-mediated carbon-fluorine bond functionalisation through cyclohexyne “umpolung”

Sara Bonfante; Theo F.N. Tanner; Christian Lorber; Jason M. Lynam; Antoine Simonneau; John M. Slattery

doi:10.1039/d4sc08522a

Zirconium-mediated carbon-fluorine bond functionalisation through cyclohexyne “umpolung”

Sara Bonfante, Theo F.N. Tanner, Christian Lorber^*, Jason M. Lynam^*, Antoine Simonneau^*, John M. Slattery^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

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.

Original language	English
Number of pages	8
Journal	Chemical Science
Early online date	16 Jan 2025
DOIs	https://doi.org/10.1039/d4sc08522a
Publication status	E-pub ahead of print - 16 Jan 2025

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Publisher Copyright:
© 2025 The Royal Society of Chemistry.

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10.1039/d4sc08522aLicence: CC BY

Zirconium-mediated carbon–fluorine bond functionalisation through cyclohexyne “umpolung”
© 2025 The Author(s).
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Cite this

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title = "Zirconium-mediated carbon-fluorine bond functionalisation through cyclohexyne “umpolung”",

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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T1 - Zirconium-mediated carbon-fluorine bond functionalisation through cyclohexyne “umpolung”

AU - Bonfante, Sara

AU - Tanner, Theo F.N.

AU - Lorber, Christian

AU - Lynam, Jason M.

AU - Simonneau, Antoine

AU - Slattery, John M.

PY - 2025/1/16

Y1 - 2025/1/16

N2 - 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.

AB - 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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DO - 10.1039/d4sc08522a

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SN - 2041-6520

JO - Chemical Science

JF - Chemical Science

ER -

Zirconium-mediated carbon-fluorine bond functionalisation through cyclohexyne “umpolung”

Abstract

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