On the stereochemical course of the addition of allylsilanes to aldehydes

Scott E. Denmark, Eric J. Weber, Neil G. Almstead, Larry M. Wolf

Research output: Contribution to journalArticlepeer-review

Abstract

Model compounds 3 and 5 have been studied to determine the orientation of the reacting double bonds in the transition state of the allylmetal-aldehyde addition. These models were designed to remove any intrinsic steric bias for the formation of the bicyclic products that would obfuscate a stereoelectronic contribution to the transition states. Model system 3 revealed a modest preference for the synclinal transition state, albeit in very low yields. Model system 5 underwent selective and largely Lewis acid independent cyclization primarily via a synclinal transition state. The high proximal selectivity observed in these cyclizations likely reflects the selectivity of an unhindered allylmetal-aldehyde addition for the synclinal transition state and results from a stereoelectronic preference, not an intrinsic steric bias, for the synclinal arrangement of double bonds.

Original languageEnglish (US)
Pages (from-to)7701-7718
Number of pages18
JournalTetrahedron
Volume68
Issue number37
DOIs
StatePublished - Sep 16 2012

Keywords

  • Aldehyde
  • Allylsilane
  • Antiperiplanar
  • Lewis acid
  • Stereochemistry
  • Synclinal

ASJC Scopus subject areas

  • Biochemistry
  • Drug Discovery
  • Organic Chemistry

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