Enantioselective ring opening of epoxides with silicon tetrachloride in the presence of a chiral lewis base: Mechanism studies

Scott E. Denmark, Paul A. Barsanti, Gregory L. Beutner, Tyler W. Wilson

Research output: Contribution to journalArticle

Abstract

The enantioselective ring opening of meso-epoxides (from both cyclic and acyclic olefins) with silicon tetrachloride under catalysis by chiral phosphoramides affords enantiomerically enriched chlorohydrins in excellent yields. Experiments designed to elucidate the mechanistic foundation and origins of enantioselectivity are described. From studies on the loading and stoichiometry of the reagent (SiCl4) and the catalyst [(R)-1] it was established that only one chloride per SiCl4 is delivered and that the nature of eactive species does not change over the course of the reaction. Kinetic studies together with asymmetric amplification experiments have suggested that more than one catalyst molecule may be bound to SiCl4 in the stereochemistry-determining transition structure.

Original languageEnglish (US)
Pages (from-to)567-582
Number of pages16
JournalAdvanced Synthesis and Catalysis
Volume349
Issue number4-5
DOIs
StatePublished - Mar 2007

Keywords

  • Asymmetric catalysis
  • C-C bond formation
  • Cross-coupling
  • Enzyme catalysis
  • Homogeneous catalysis

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

Fingerprint Dive into the research topics of 'Enantioselective ring opening of epoxides with silicon tetrachloride in the presence of a chiral lewis base: Mechanism studies'. Together they form a unique fingerprint.

  • Cite this