Tandem Insertion of Halocarbenoids and Lithium Acetylides into Zirconacycles: A Novel Rearrangement to Zirconium Alkenylidenates by β-Addition to an Alkynyl Zirconocene

Authors

  • Dr. Jozef Stec,

    1. School of Chemistry, University of Southampton, Highfield, Southampton, Hampshire SO17 1BJ (UK), Fax: (+44) 23-80593781
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  • Dr. Emma Thomas,

    1. School of Chemistry, University of Southampton, Highfield, Southampton, Hampshire SO17 1BJ (UK), Fax: (+44) 23-80593781
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  • Dr. Sally Dixon,

    1. School of Chemistry, University of Southampton, Highfield, Southampton, Hampshire SO17 1BJ (UK), Fax: (+44) 23-80593781
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  • Prof. Richard J. Whitby

    Corresponding author
    1. School of Chemistry, University of Southampton, Highfield, Southampton, Hampshire SO17 1BJ (UK), Fax: (+44) 23-80593781
    • School of Chemistry, University of Southampton, Highfield, Southampton, Hampshire SO17 1BJ (UK), Fax: (+44) 23-80593781
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Abstract

Tandem insertion of 1,1-dihalo-1-lithio species (halocarbenoids) and lithium alkynides into zirconacyclopentenes and zirconcyclopentanes affords carbocyclic products in high yields via an unusual rearrangement that probably involves addition of an organolithium species to the β-position of a zirconium–alkyne complex to give an alkenylidene–zirconate species. A wide variety of cyclopentanoid organic structures are rapidly assembled in good yield using this multicomponent coupling. The main side reaction, which becomes exclusive in some cases, is β-hydride elimination of an intermediate cyclopentyl- or cyclopentenyl zirconocene.

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