Epoxidation and Bis-hydroxylation of C-Phenyl-？2,3-glycopyranosides.docVIP

Molecules 2005, 10, 859-870 molecules ISSN 1420-3049 Epoxidation and Bis-hydroxylation of C-Phenyl-?2,3-glyco- pyranosides. Ghada Fakha and Denis Sinou* Laboratoire de Synthèse Asymétrique, UMR 5181, CPE Lyon, Université Claude Bernard Lyon 1, 43, Boulevard du 11 novembre 1918, 69622 Villeurbanne, France. Tel. +33 (0)472448183, Fax +33 (0)478898914 * Author to whom correspondence should be addressed; e-mail sinou@univ-lyon1.fr Received: 1 October 2004; in revised form 13 October 2004 / Accepted: 15 October 2004 / Published: 31 August 2005 Abstract: Epoxidation and cis-hydroxylation of C-phenyl-?2,3-glycopyranosides have been carried out with a view to developing C-aryl glycoside synthesis. Epoxidation of (2,3- dideoxy-D-erythro-hex-2-enopyranosyl)benzene and (6-O-tert-butyldimethylsilyl-2,3- dideoxy-D-erythro-hex-2-enopyranosyl)benzene gave predominantly the allo-adducts whatever the configuration at the anomeric center. Epoxidation of (4,6-di-O-tert-butyl- dimethylsilyl-2,3-dideoxy-D-erythro-hex-2-enopyranosyl)benzene gave the manno- and allo-adducts in a 89:11 and 40:60 ratios for the α- and β-anomers, respectively. Hydroxylation of α-C-phenyl-?2,3-glycopyranosides using OsO4 afforded the manno-adduct only, whatever the substituents at positions 4 and 6, whereas hydroxylation of (2,3-dideoxy- β-D-erythro-hex-2-enopyranosyl)benzene and (4,6-di-O-tert-butyldimethylsilyl-2,3- dideoxy- β-D-erythro-hex-2-enopyranosyl)benzene gave the manno- and allo-adducts in 25:75 and 80:20 ratios, respectively. Keywords: (2,3-Unsaturated-glycopyranosyl)benzene, epoxidation, cis-hydroxylation. Introduction There is a great interest in C-aryl glycosides. This is due to their occurrence in many natural products possessing important medicinal and therapeutic properties [1-3], as well as to their use as valuable chiral building blocks [4-6]. However, it is important to obtain