title: From D-glucuronic acid to L-iduronic acid derivatives via a radical tandem decarboxylation-cyclization.
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.
authors: Université 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.
authors: Stéphane
authors: S
authors: Salamone
authors: Université 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.
authors: Michel
authors: M
authors: Boisbrun
authors: Université de Lorraine, CRM2, UMR 7036, BP 70239, F-54506 Vandœuvre-lès-Nancy, France; CNRS, CRM2, UMR 7036, BP 70239, F-54506 Vandœuvre-lès-Nancy, France.
authors: Claude
authors: C
authors: Didierjean
authors: Université 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. Electronic address: yves.chapleur@univ-lorraine.fr.
authors: Yves
authors: Y
authors: Chapleur
mesh_terms: D002236:Carbohydrate Conformation; D018360:Crystallography, X-Ray; D003500:Cyclization; D003653:Decarboxylation; D005609:Free Radicals / Q000737:chemistry*; D005965:Glucuronates / Q000737:chemistry*; D007067:Iduronic Acid / Q000031:analogs & derivatives* / Q000138:chemical synthesis*; D009844:Oligosaccharides / Q000138:chemical synthesis*; D010084:Oxidation-Reduction
chemical_list: D005609:Free Radicals; D005965:Glucuronates; D009844:Oligosaccharides; D007067:Iduronic Acid; C479958:idraparinux
keywords: C-5 inversion; Radical cyclization; Radical decarboxylation; l-Idose