Rapid transformation of D-mannose into orthogonally protected D-glucosamine and D-galactosamine thioglycosides

J Org Chem. 2011 Jun 3;76(11):4703-9. doi: 10.1021/jo200342v. Epub 2011 May 3.

Abstract

An expedient protocol for synthesis of orthogonally protected 2-azido-2-deoxy-D-glucosamine and 2-azido-2-deoxy-D-galactosamine donors from D-mannose is described. Readily available phenyl β-D-thiomannoside is rapidly transformed into D-GlcN(3) thioglycosides via a highly regioselective 3-O-acylation followed by 4,6-O-benzylidenation and azide displacement of C2-OTf, which is further converted into D-GalN(3) thioglycosides through Lattrell-Dax inversion of the C4 hydroxy group and its Boc protection. The reaction sequence may be completed in 2 days and involves simple workups and minimal column chromatography.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Formic Acid Esters / chemistry
  • Galactosamine / chemistry*
  • Glucosamine / chemistry*
  • Kinetics
  • Mannose / chemistry*
  • Stereoisomerism
  • Substrate Specificity
  • Thioglycosides / chemistry*

Substances

  • Formic Acid Esters
  • Thioglycosides
  • t-butyloxycarbonyl group
  • Galactosamine
  • Glucosamine
  • Mannose