Practical Synthesis of 4'-Thioribonucleosides from L-Arabinose via Novel Reductive Ring-Contraction Reaction and Pummerer-Type Thioglycosylation

Curr Protoc Nucleic Acid Chem. 2017 Dec 24:71:1.43.1-1.43.12. doi: 10.1002/cpnc.45.

Abstract

The detailed practical synthesis of 4'-thionucleosides starting from L-arabinose is described here. 1,4-Anhydro-2,3-O-isopropylidene-4-thioribitol, which is the key intermediate for the synthesis of 4'-thionucleosides, is obtained from L-arabinose in several steps, including a novel reductive ring-contraction reaction. After oxidation of the key intermediate, the sulfoxide is subjected to Pummerer-type thioglycosylation in the presence of persilylated nucleobases to obtain the 4'-thioribonucleosides in good yield and β-selectively. © 2017 by John Wiley & Sons, Inc.

Keywords: 4-thioribonucleosides; 4-thiosugar; L-arabinose; Pummerer reaction; reductive ring contraction.

MeSH terms

  • Arabinose / chemistry*
  • Glycosylation
  • Oxidation-Reduction
  • Ribonucleosides / chemical synthesis*
  • Structure-Activity Relationship
  • Thionucleosides / chemical synthesis*

Substances

  • Ribonucleosides
  • Thionucleosides
  • Arabinose