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Tandem Insertion of Halocarbenoids and Lithium Acetylides into Zirconacycles: A Novel Rearrangement to Zirconium Alkenylidenates by β‐Addition to an Alkynyl Zirconocene
Author(s) -
Stec Jozef,
Thomas Emma,
Dixon Sally,
Whitby Richard J.
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201002962
Subject(s) - lithium (medication) , chemistry , tandem , zirconium , yield (engineering) , alkyne , medicinal chemistry , hydride , organic chemistry , catalysis , materials science , metal , medicine , metallurgy , composite material , endocrinology
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.