Bonfante, Sara, Tanner, Theo F.N., Lorber, Christian et al. (3 more authors) (2025) Zirconium-mediated carbon-fluorine bond functionalisation through cyclohexyne “umpolung”. Chemical Science. ISSN 2041-6539
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.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | Publisher Copyright: © 2025 The Royal Society of Chemistry. |
Dates: |
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Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Funding Information: | Funder Grant number EUROPEAN COMMISSION 860322 |
Depositing User: | Pure (York) |
Date Deposited: | 05 Feb 2025 10:50 |
Last Modified: | 05 Feb 2025 10:50 |
Published Version: | https://doi.org/10.1039/d4sc08522a |
Status: | Published online |
Refereed: | Yes |
Identification Number: | 10.1039/d4sc08522a |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:222924 |
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Filename: d4sc08522a.pdf
Description: Zirconium-mediated carbon–fluorine bond functionalisation through cyclohexyne “umpolung”
Licence: CC-BY 2.5