Regio- and stereocontrolled synthesis of novel steroidal isoxazolines: a new route to the formation of selectively modified steroid side chains

Steroids. 2013 Sep;78(9):823-31. doi: 10.1016/j.steroids.2013.04.017. Epub 2013 May 7.

Abstract

1,3-Dipolar cycloaddition reaction of acetonitrile oxide to cis- and trans-22-hydroxy-24-alkoxycarbonyl-Δ(23)-steroids is investigated. An unusual stereochemical course of the cycloaddition, leading to the same set of the isoxazoline adducts for both (Z)- and (E)-disubstituted olefins is revealed. It is shown, the reaction is regioselective and all possible 4',5'-diastereoisomers of resulting isoxazolines can be prepared as major products by cycloaddition to the suitable alkene. The structure of the key compounds is confirmed by X-ray and 2D NMR analysis.

Keywords: Brassinosteroids; Isoxazolines; Nitrile oxides.

MeSH terms

  • Acetonitriles / chemistry
  • Brassinosteroids / chemical synthesis*
  • Cycloaddition Reaction
  • Isoxazoles / chemical synthesis*
  • Magnetic Resonance Spectroscopy
  • Models, Molecular
  • Molecular Conformation
  • Stereoisomerism

Substances

  • Acetonitriles
  • Brassinosteroids
  • Isoxazoles
  • acetonitrile oxide