Synthetic studies toward pyruvate acetal-containing saccharides: en route to the efficient synthesis of Rhizobium-related exopolysaccharide fragments.
The disaccharide building block benzyl O-(2,3-di-O-benzoyl-4,6-O-[(R)-1-(methoxycarbonyl) ethylidene]-beta-D-galactopyranosyl)-(1-->3)-2-O-benzoyl-4,6-O-[(S)-1- (methoxycarbonyl)ethylidene]-alpha-D-glucopyranoside (13), related to a Rhizobium exopolysaccharide, was prepared by coupling various 4,6-O-[(R)-1-(methoxycarbonyl)ethylidene]-D-galactosyl donors (benzoyl-protected chloride 1, pivaloyl-protected chloride 2, and benzoyl-protected fluorides 3 and 4, and trichloroacetimidate 5) with benzyl 2-O-benzoyl-4,6-O-[(S)-1- (methoxycarbonyl)ethylidene]-alpha-D-glucopyranoside (10) and the corresponding 2,3-O-tetraisopropyldisiloxane-protected glucoside 12. The best results, with respect to beta-selectivity and yield of the coupling, were obtained with 5 and 10 in dichloromethane. The beta-linked (13) and alpha-linked (14) disaccharides were efficiently converted via the 1-OH derivatives 17 and 21 into the corresponding trichloroacetimidates 18 and 22. The latter were used for the synthesis of the disaccharide ligands 4,6-(R)-pyruvate-beta-D-Galp-(1-->3)-4,6-(S)-pyruvate-beta-D-Glcp-O(CH2) 5NH2 (20), and 4,6-(R)-pyruvate-alpha-D-Galp-(1-->3)-4,6-(S)-pyruvate-beta-D-Glcp-O (CH2)5NH2 (24). The corresponding tri- and tetra-saccharide derivatives 4,6-(R)-pyruvate-beta-D-Galp-(1-->3)-4,6-(S)-pyruvate-beta-D-Glcp-(1-->4 )-beta- D-Glcp-O(CH2)5NH2 (28) and 4,6-(R)-pyruvate-beta-D-Galp-(1-->3)-4,6-(S)-pyruvate-beta-D-Glcp-(1-->4 )-beta- D-Glcp-(1-->4)-beta-D-Glcp-O(CH2)25NH2 (36) were obtained similarly.
Eckhardt
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Institut für Organische Chemie und Isotopenforschung, Universität Stuttgart, Germany.
Ziegler
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D002236:Carbohydrate Conformation; D002240:Carbohydrate Sequence; D004187:Disaccharides / Q000138:chemical synthesis* / Q000737:chemistry; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D008969:Molecular Sequence Data; D015394:Molecular Structure; D009904:Optical Rotation; D011135:Polysaccharides, Bacterial / Q000737:chemistry*; D012231:Rhizobium; D013329:Structure-Activity Relationship
D004187:Disaccharides; D007202:Indicators and Reagents; D011135:Polysaccharides, Bacterial