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

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 [beta]-position of a zi...

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Bibliographic Details
Published inChemistry : a European journal Vol. 17; no. 17; p. 4896
Main Authors Stec, Jozef, Thomas, Emma, Dixon, Sally, Whitby, Richard J
Format Journal Article
LanguageEnglish
Published Weinheim Wiley Subscription Services, Inc 18.04.2011
Subjects
Chemistry
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Summary: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 [beta]-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 [beta]-hydride elimination of an intermediate cyclopentyl- or cyclopentenyl zirconocene.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201002962