Synthesis of ansa-titanocenes via a double-Skattebøl rearrangement

Scott C. Sutton, Michael H. Nantz, Sean R. Parkin

Research output: Contribution to journalArticle

24 Scopus citations

Abstract

Novel synthetic approaches to chiral ethylene-bridged ansa-titanocenes possessing stereogenic centers on the bridging carbon chain are described. A key step in the preparation of these compounds is the double-Skattebøl rearrangement of bis(vinyldibromocyclopropane) intermediates derived from 1,4-disulfones. The influence of tether substitution on the diastereoselection in ansa-titanocene formation has been examined through stereospecific 2,3-dimethyl substitution on the ethylene bridge of β-methyl-substituted bis(cyclopentadienyl) ligands. The ethylene-bridged bis(cyclopentadienes) were converted to their dilithium salts and treated with TiCl3·3THF to afford mixtures of meso and racemic ansa-titanocenes. Several isomers were isolated, and their structures were determined by X-ray diffraction. The meso configuration of tether-methyl substituents was found to promote the formation of a racemic configuration of β-methyl cyclopentadienide ligands whereas the racemic configuration of tether-methyl substituents was found to have little effect on the racemic to meso ratio relative to ethylenebis-[η5-1-(3-methylcyclopentadienyl)] titanium dichloride. The spectral and physical characteristics of these compounds are discussed.

Original languageEnglish (US)
Pages (from-to)2248-2257
Number of pages10
JournalOrganometallics
Volume12
Issue number6
StatePublished - 1993

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

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    Sutton, S. C., Nantz, M. H., & Parkin, S. R. (1993). Synthesis of ansa-titanocenes via a double-Skattebøl rearrangement. Organometallics, 12(6), 2248-2257.