Biomimetic synthesis of acid-sensitive (-)-caparrapi oxide and (+)-8-epicaparrapi oxide induced by artificial cyclases

Org Lett. 2005 Apr 14;7(8):1601-4. doi: 10.1021/ol050295r.

Abstract

[reaction: see text] Asymmetric total syntheses of acid-sensitive (-)-caparrapi oxide (1) and (+)-8-epicaparrapi oxide (2) from farnesol (9) were achieved using Sharpless-Katsuki epoxidation and Lewis acid-assisted chiral Bronsted acid (chiral LBA)-induced polyene cyclization as key steps. Furthermore, (-)-1 could be directly synthesized from (S)-nerolidol (3) and (R)-LBA with 88% ds by reagent control which overcame substrate control, while (-)-2 was obtained from (R)-3 and (R)-LBA with >99% ds by the double-asymmetric induction.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acids / chemistry*
  • Enzymes / metabolism*
  • Molecular Mimicry*
  • Molecular Structure
  • Oxides / chemical synthesis*
  • Sesquiterpenes / chemical synthesis*
  • Spectrum Analysis
  • Stereoisomerism

Substances

  • 8-epicaparrapi oxide
  • Acids
  • Enzymes
  • Oxides
  • Sesquiterpenes
  • caparrapi oxide
  • nerolidol