Warren C D, Milat M L, Augé C, Jeanloz R W
Carbohydr Res. 1984 Mar 1;126(1):61-80. doi: 10.1016/0008-6215(84)85126-5.
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".
合成的苄基 O-(2,3,4,6-四-O-乙酰基-β-D-吡喃甘露糖基)-(1→4)-(2-乙酰氨基-3,6-二-O-乙酰基-2-脱氧-β-D-吡喃葡萄糖基)-(1→4)-2-乙酰氨基-3,6-二-O-苄基-2-脱氧-α-D-吡喃葡萄糖苷，通过苄基的催化氢解，接着用乙酰氯-氯化氢处理，然后进行“氯离子催化”，转化为 O-(2,3,4,6-四-O-乙酰基-β-D-吡喃甘露糖基)-(1→4)-O-(2-乙酰氨基-3,6-二-O-乙酰基-2-脱氧-β-D-吡喃葡萄糖基)-(1→4)-2-甲基-(3,6-二-O-乙酰基-1,2-二脱氧-α-D-吡喃葡萄糖基)-[2,1-d]-2-恶唑啉。该化合物在严格无水条件下用二苄基磷酸处理进行磷酸化，经催化氢解后得到全乙酰化三糖磷酸酯。将其与 P1-多萜醇 P2-二苯基二磷酸酯偶联，经 O-脱乙酰化后得到 P1-多萜醇 P2-[O-β-D-吡喃甘露糖基-(1→4)-O-(2-乙酰氨基-2-脱氧-β-D-吡喃葡萄糖基)-(1→4)-2-乙酰氨基-2-脱氧-α-D-吡喃葡萄糖基]二磷酸酯，一种三糖“脂质中间体”。从甘露糖苷尿中分离得到的 O-α-D-吡喃甘露糖基-(1→3)-O-β-D-吡喃甘露糖基-(1→4)-2-乙酰氨基-2-脱氧-D-葡萄糖合成的 O-(2,3,4,6-四-O-乙酰基-α-D-吡喃甘露糖基)-(1→3)-O-(2,4,6-三-O-乙酰基-β-D-吡喃甘露糖基)-(1→4)-O-(2-乙酰氨基-3,6-二-O-乙酰基-2-脱氧-β-D-吡喃葡萄糖基)-(1→4)-(2-乙酰氨基-3,6-二-O-乙酰基-2-脱氧-α-D-吡喃葡萄糖基)磷酸酯，与 P1-多萜醇 P2-二苯基二磷酸酯偶联，经 O-脱乙酰化后得到 P1-多萜醇 P2-[O-α-D-吡喃甘露糖基-(1→3)-O-β-D-吡喃甘露糖基-(1→4)-O-(2-乙酰氨基-2-脱氧-β-D-吡喃葡萄糖基)-(1→4)-2-乙酰氨基-2-脱氧-α-D-吡喃葡萄糖基]二磷酸酯，一种四糖“脂质中间体”。
