Tandem Insertion of Halocarbenoids and Lithium Acetylides into Zirconacycles: A Novel Rearrangement to Zirconium Alkenylidenates by Delta b-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 Delta *b-position of a...

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Bibliographic Details
Published in:Chemistry : a European journal 2011-04, Vol.17 (17), p.4896-4904
Main Authors: Stec, Jozef, Thomas, Emma, Dixon, Sally, Whitby, Richard J
Format: Article
Language:English
Subjects:
Insertion
Joining
Lithium
Zirconium
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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 Delta *b-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 Delta *b-hydride elimination of an intermediate cyclopentyl- or cyclopentenyl zirconocene.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201002962