A straightforward and flexible [4 + 2] route to beta-C-naphthyl-2-deoxy-glycosides through tandem hydroboration-ketal reduction: de novo access to C-naphthyl-6-fluoro and 6,6-difluoro 2-deoxyglycosides

J Org Chem. 2005 Apr 1;70(7):2641-50. doi: 10.1021/jo048042j.

Abstract

[reaction: see text] Under standard hydroboration-oxidation conditions, the dihydropyrans 4 underwent a highly stereocontrolled tandem reaction, involving the expected hydration of the double bond together with the reduction of the ketal moiety. This unprecedented transformation gives rise to a short, [4 + 2]-based synthetic route to (+/-)-beta-C-naphthyl-2-deoxyglycosides 5, which allows a significant structural and functional diversity at C-6. We thus described the first synthesis of (+/-)-C-aryl-6-fluoro and -6,6-difluoro olivosides, via the allylic mono- and difluorides produced by regioselective fluorination of, respectively, hydroxyalkyl and oxoalkyl dihydropyran derivatives.

MeSH terms

  • Glycosides / chemical synthesis*
  • Glycosides / chemistry
  • Magnetic Resonance Spectroscopy
  • Oxidation-Reduction

Substances

  • Glycosides