title: The synthesis of a trisaccharide and a tetrasaccharide lipid intermediate. P1-dolichyl P2-[O-beta-D-mannopyranosyl-(1----4)-O-(2-acetamido-2-deoxy- beta-D-glucopyranosyl)-(1----4)-2-acetamido-2-deoxy-alpha-D- glucopyranosyl] diphosphate and P1-dolichyl P2-[O-alpha-D-mannopyranosyl-(1----3)-O-beta-D- mannopyranosyl-(1----4)-O-(2-acetamido-2-deoxy-beta-D-glucopyranosyl)- (1----4)-2-acetamido-2-deoxy-alpha-D-glucopyranosyl] diphosphate.
abstract: Synthetic benzyl O-(2,3,4,6,-tetra-O-acetyl-beta-D-mannopyranosyl)-(1-4)- (2-acetamido-3,6-di-O-acetyl-2-deoxy-beta-D-glucopyranosyl)-(1-4)- 2-acetamido-3,6-di-O-benzyl-2-deoxy-alpha-D-glucopyranoside was converted, by catalytic hydrogenolysis of the benzyl groups, followed by treatment with acetyl chloride-hydrogen chloride and then "chloride-ion catalysis", into O-(2,3,4,6-tetra-O-acetyl- beta-D-mannopyranosyl)-(1-4)-O-(2-acetamido-3,6-di-O-acetyl-2-deoxy beta- D-glucopyranosyl)- (1-4)-2-methyl-(3,6-di-O-acetyl-1,2-dideoxy-alpha-D- glucopyrano)-[2,1-d]-2-oxazoline. This compound was phosphorylated by treatment with dibenzyl phosphate under strictly anhydrous conditions to give after catalytic hydrogenolysis, a peracetyl trisaccharide phosphate. This was coupled with P1-dolichyl P2-diphenyl diphosphate to give, after O-deacetylation, P1-dolichyl P2-[O- beta-D-mannopyranosyl- (1-4)-O-(2-acetamido-2-deoxy-beta-D-glucopyranosyl)- (1-4)-2-acetamido-2-deoxy-alpha-D-glucopyranosyl] diphosphate, a trisaccharide "lipid intermediate". O-(2,3,4,6-Tetra-O-acetyl-alpha-D-mannopyranosyl)-(1-3)-O-(2,4,6-tri-O- acetyl-beta-D-mannopyranosyl)-(1-4)-O-(2-acetamido-3,6-di-O-acetyl-2- deoxy-beta- D-glucopyranosyl)- (1-4)-(2-acetamido-3,6-di-O-acetyl-2-deoxy-alpha-D-glucopyranosyl) phosphate, synthesized from O-alpha-D-mannopyranosyl-(1-3)-O-beta-D- mannopyranosyl-(1-4)-2-acetamido-2-deoxy-D-glucopyranose that had been isolated from mannosidosis urine was coupled with P1-dolichyl P2-diphenyl diphosphate to give, after O-deacetylation, P1-dolichyl P2-[O-alpha-D-mannopyranosyl- (1-3)-O-beta-D-mannopyranosyl-(1-4)-O-(2-acetamido-2-deoxy-beta-D- glucopyranosyl)-(1-4)-2-acetamido-2-deoxy-alpha-D-glucopyranosyl] diphosphate, a tetrasaccharide "lipid intermediate".
mesh_terms: D002855:Chromatography, Thin Layer; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D009844:Oligosaccharides / Q000138:chemical synthesis*; D009904:Optical Rotation; D011105:Polyisoprenyl Phosphate Sugars / Q000138:chemical synthesis*; D013055:Spectrophotometry, Infrared
chemical_list: D007202:Indicators and Reagents; D009844:Oligosaccharides; D011105:Polyisoprenyl Phosphate Sugars