From D-glucuronic acid to L-iduronic acid derivatives via a radical tandem decarboxylation-cyclization
Stéphane Salamone1, Michel Boisbrun1, Claude Didierjean2
1Université de Lorraine, SRSMC, UMR 7565, BP 70239, F-54506 Vandœuvre-lès-Nancy, France; CNRS, SRSMC, UMR 7565, BP 70239, F-54506 Vandœuvre-lès-Nancy, France.
Abstract:
A synthesis to L-iduronic derivatives, major components of heparin derived pentasaccharides was accomplished by formal inversion of configuration at C-5 of a D-glucuronic acid derivative through radical formation at C-5 using Barton decarboxylation followed by intramolecular radical addition on an acetylenic tether at O-4 giving exclusively a bicyclic sugar of L-ido configuration. Oxidation and ring opening of this bicyclic sugar led to a L-iduronate. This method opens the way to short syntheses of pentasaccharidic moiety of Idraparinux and congeners.
Related Concept Videos
Phase II Reactions: Glucuronidation
Loss of Carboxy Group as CO2: Decarboxylation of Malonic Acid Derivatives
Drug Metabolism: Phase II Reactions
Oligosaccharide Assembly
Multiple sugar molecules that may or may...
Biosynthesis of Polysaccharides
Alkylation of β-Diester Enolates: Malonic Ester Synthesis


