Synthèse de l'acide 5-acétamido-3,5-didésoxy-4-O-méthyl-D-glycéro-D-galacto-2-nonulosonique (acide 4-O-méthyl-N-acétylneuraminique). Partie II

Abstract

3-Acetamido-3-deoxy-4,5:6,7-di-O-isopropylidene-D-glycero-D-galacto-heptose diethyl dithioacetal was transformed into 3-acetamido-3-deoxy-4,5:6,7-di-O-isopro-pylidene-2-O-methyl-aldehydro-D-glycero-D-galacto-heptose after O-methylation followed by desulfuration. A Wittig reaction with an excess of [ethoxy(ethoxycarbonyl)-methylene]triphenylphosphorane in the presence of benzoic acid gave a mixture of ethyl 5-acetamido-3.5-dideoxy-2-O-ethyl-6,7:8,9-di-O-isopropylidene-4-O-methyl-D-glycero-D-galacto-non-2-enonate (23 %) and the D-glycero-D-talo (22 %) isomer. An ethoxymercuration-demercuration reaction, followed by acid hydrolysis, converted the former into ethyl 4-O-methyl-N-acetylneuraminate and the latter into the C-4 stereoisomer. 4-O-Methyl-N-acetylneuraminic acid was then obtained in crystalline form, and its structure ascertained by mass spectrometry and 1H- and 13C-nuclear magnetic resonance