Chemistry: A European Journal 2011-04-18

Tandem insertion of halocarbenoids and lithium acetylides into zirconacycles: a novel rearrangement to zirconium alkenylidenates by β-addition to an alkynyl zirconocene.

Jozef Stec, Emma Thomas, Sally Dixon, Richard J Whitby

Index: Chemistry 17(17) , 4896-904, (2011)

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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.Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.