Synthesis of the tetrasaccharide lipid intermediate P1-dolichyl P2-[O-alpha-D-mannopyranosyl-(1----6)-O-beta-D-mannopyranosyl-(1----4) -O-(2- acetamido-2-deoxy-beta-D-glucopyranosyl)-(1----4)-2-acetamido-2- deoxy-alpha-D-glucopyranosyl] diphosphate.
O-alpha-D-Mannopyranosyl-(1----6)-O-beta-D-mannopyranosyl-(1----4)-O-(2- acetamido-2-deoxy-beta-D-glucopyranosyl)-(1----4)-2-acetamido-2-deoxy- D-glucopyranose was isolated from bovine or ovine mannosidosis urine. After peracetylation, treatment with trimethylsilyl trifluoromethanesulfonate gave a high yield of a peracetyl oxazoline, which was phosphorylated with dibenzyl phosphate to give a dibenzyl glycosyl phosphate that was converted into a peracetyl tetrasaccharide phosphate by catalytic hydrogenolysis. A coupling reaction with P1-dolichyl P2-diphenyl diphosphate, prepared in two stages from pig-liver dolichol, yielded a peracetyl diphosphoric diester, which on O-deacetylation gave P1-dolichyl P2-[O-alpha-D-mannopyranosyl-(1----6)-O-beta-D-mannopyranosyl-(1----4)-O -(2- acetamido-2-deoxy-beta-D-glucopyranosyl)-(1----4)-2-acetamido-2-deoxy- alpha-D- glucopyranosyl] diphosphate. This tetrasaccharide lipid intermediate was active as an acceptor of D-mannose residues from GDP-D-mannose in the presence of calf pancreas microsomes.
Department of Biological Chemistry, Harvard Medical School, Boston, Massachusetts.
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Warren
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Nakabayashi
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Jeanloz
D000107:Acetylation; D000818:Animals; D002236:Carbohydrate Conformation; D002240:Carbohydrate Sequence; D004288:Dolichol Phosphates / Q000302:isolation & purification; D007202:Indicators and Reagents; D008099:Liver; D009682:Magnetic Resonance Spectroscopy; D009844:Oligosaccharides / Q000138:chemical synthesis; D009904:Optical Rotation; D011105:Polyisoprenyl Phosphate Sugars / Q000138:chemical synthesis*; D013552:Swine
D004288:Dolichol Phosphates; D007202:Indicators and Reagents; D009844:Oligosaccharides; D011105:Polyisoprenyl Phosphate Sugars