Developments in the Simmons-Smith-mediated epoxidation reaction

VK Aggarwal*, Michael P Coogan, Rachel A Stenson, Raymond VH Jones, Robin Fieldhouse, John Blacker

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

40 Citations (Scopus)

Abstract

The reaction between Et2Zn, CICH2I, sulfide, and aldehyde furnishes terminal epoxides in high yields. The reaction occurs via a zinc carbenoid, which reacts with the sulfide to furnish an ylide, which in turn reacts with the aldehyde to give the epoxide. Chiral ligands capable of chelation to zinc [1,2-amino alcohols, amino acids, bis(oxazolines), taddols] were examined, but only low enantioselectivity was observed (up to 11% ee). A number of chiral sulfides were also examined, but again only low enantioselectivity was observed (up to 16% ee). However, linking a sulfide to a metal capable of chelation to zinc [a bis(oxazoline) bearing a sulfide at the 5 position] produced a reagent that gave up to 54% ee in the epoxidation process. The same system was applied to the preparation of terminal aziridines from imines. The optimum group on nitrogen was a sulfonyl group, although groups capable of chelation of zinc (o-methoxyphenyl) were also effective. Attempts to render the aziridination process asymmetric by using the above strategy were less successful (up to 19% ee).

Translated title of the contributionDevelopments in the Simmons-Smith Mediated Epoxidation Reaction
Original languageEnglish
Pages (from-to)319-326
Number of pages8
JournalEuropean Journal of Organic Chemistry
Issue number2
Publication statusPublished - Jan 2002

Keywords

  • aziridines
  • bisoxazolines
  • carbenoids
  • sulfur
  • terminal epoxides
  • ylides
  • zinc
  • CATALYTIC ASYMMETRIC EPOXIDATION
  • KINETIC RESOLUTION
  • TERMINAL EPOXIDES
  • ALLYLIC ALCOHOLS
  • ONE-POT
  • ALDEHYDES
  • CYCLOPROPANATION
  • EFFICIENT
  • REAGENTS
  • SULFIDES

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