Silicon‐Directed Nazarov Reactions III. Stereochemical and Mechanistic Considerations

Todd K. Jones, Scott E. Denmark

Research output: Contribution to journalArticlepeer-review

Abstract

The influence of remote substituents on the stereochemical outcome of electrocyclization in the silicon‐directed Nazarov reaction has been examined. While the degree of stereocontrol was modest (ca. 3:1) the substituent in the major isomer (4,5 or 7‐substituted cis‐hexahydroind‐2‐en‐1‐ones) is always cis to the protons on the ring fusion. Thorough spectroscopic and conformational analysis revealed that divergent senses of electrocyclization are responsible for the observed products. Additional experiments suggest that steric, rather than stereoelectronic forces control the sense of cyclization. A qualitative description of the nature of reactive intermediates in the silicon‐directed Nazarov reaction is proposed as well as an explanation for the remarkable efficacy of FeCl3 for inducing the reaction.

Original languageEnglish (US)
Pages (from-to)2397-2411
Number of pages15
JournalHelvetica Chimica Acta
Volume66
Issue number8
DOIs
StatePublished - 1983

ASJC Scopus subject areas

  • Catalysis
  • Biochemistry
  • Drug Discovery
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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