Addition of malonyl radicals to glycals with C-1 acceptor groups: remarkable influence of the substituents on the product distribution

Chem Commun (Camb). 2002 Jun 21:(12):1294-5. doi: 10.1039/b202898k.

Abstract

The ceric(IV) ammonium nitrate (CAN)-mediated radical addition of dimethyl malonate to glycals 1 affords methyl glycosides 2 and ortho esters 3 as main products; the product distribution strongly depends on the substitution pattern at the 1-position, which can be rationalized in terms of the oxidation potentials of the intermediary anomeric radicals.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Catalysis
  • Cerium
  • Galactose / analogs & derivatives*
  • Galactose / chemistry
  • Glycosides / chemical synthesis*
  • Indicators and Reagents
  • Magnetic Resonance Spectroscopy
  • Malonates / chemistry*
  • Monosaccharides / chemistry*
  • Oxidation-Reduction

Substances

  • Glycosides
  • Indicators and Reagents
  • Malonates
  • Monosaccharides
  • galactal
  • Cerium
  • ceric ammonium nitrate
  • Galactose