Diastereoselective silacyclopropanations of functionalized chiral alkenes

Tom G. Driver, Annaliese K. Franz, K. A. Woerpel

Research output: Contribution to journalArticle

Abstract

Lithium reduction of di-tert-butyldichlorosilane and thermal silylene transfer (105-125 °C) are complementary methods for the highly diastereoselective silacyclopropanations of a range of functionalized chiral olefins to afford complex silacycles. We have shown that functionalized cyclohexenes, cyclopentenes, norbornenes, and 1,1-disubstituted alkenes undergo silacyclopropanation with excellent diastereoselectivity (92:8 to ≥99:1). Our results demonstrate that steric interactions, rather than oxygen-directing effects, control the approach of the silylene or silylenoid intermediate to the olefin. We believe that the sterically demanding nature of the di-tert-butylsilylene species prevents coordination to the oxygen functionality. Thermal silylene transfer conditions exhibit broad functional group tolerance; the elevated temperatures for silylene transfer, however, cannot be employed for the silacyclopropanation of substituted cyclohexenes and 1,1-disubstituted alkenes. Elaboration of the resulting functionalized silacyclopropanes provides an efficient route to polyoxygenated products.

Original languageEnglish (US)
Pages (from-to)6524-6525
Number of pages2
JournalJournal of the American Chemical Society
Volume124
Issue number23
DOIs
StatePublished - Jun 12 2002

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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