Toepfer A, Schmidt R R
Fakultät für Chemie, Universität Konstanz, F.R.G.
Carbohydr Res. 1990 Jul 15;202:193-205. doi: 10.1016/0008-6215(90)84080-e.
2-Azido-2-deoxy-4,6-O-isopropylidene-3-O-[(1R)-(methoxycarbonyl)ethyl]- alpha-D-glucopyranosyl trichloroacetimidate (3 alpha) has been used as the glycosyl donor in the synthesis of glycosphingolipids 14 and 27. Reaction of 3 alpha with (2S, 3R, 4E)-2-azido-3-benzoyloxy-4-octadecen-1-ol (6) gave (2S, 3R, 4E)-2-azido-1-(2-azido-2-deoxy-4,6-O-isopropylidene-3-O-[(1R)-1-(m ethoxycarbonyl)ethyl]-beta-D-glucopyranosyloxyl)-3-benzoyloxy-4- octadecene (7), which was converted into (2S, 3R, 4E)-1-(2-deoxy-2-hexadecanoylamino-3-O-[(2R)-propanoyl-(L-alanyl-D -isoglutamine benzyl ester)-2-yl]-beta-D-glucopyranosyloxy)-2-hexadecanoylamino-4-oc tadecen-ol (14). Reaction of 3 alpha with tert-butyldimethylsilyl 2-azido-3,6-di-O-benzyl-2-deoxy-beta-D-glucopyranoside (15) gave tert-butyldimethylsilyl 2-azido-4-O-(2-azido-2-deoxy-4,6-O-isopropylidene-3-O-[(1R)-1-(methox ycarbonyl)ethyl]-beta-D-glucopyranosyl)-3,6-di-O-benzyl-2-deoxy-be ta- D-gluc opyranoside (16 beta), which was converted into 1,3,6-tri-O-acetyl-2-deoxy-4-O-(4,6-di-O-acetyl-2-deoxy-2-hexadecanoy lam ino-3-O-[2R)-propanoyl-(L-alanyl-D-isoglutamine methyl ester)-2-yl]-beta-D-glucopyranosyl)-2-hexadecanoylamino-D-glucopyranose (27).
2-叠氮基-2-脱氧-4,6-O-异亚丙基-3-O-[(1R)-(甲氧基羰基)乙基]-α-D-吡喃葡萄糖基三氯乙酰亚胺酯(3α)已被用作糖鞘脂14和27合成中的糖基供体。3α与(2S,3R,4E)-2-叠氮基-3-苯甲酰氧基-4-十八碳烯-1-醇(6)反应得到(2S,3R,4E)-2-叠氮基-1-(2-叠氮基-2-脱氧-4,6-O-异亚丙基-3-O-[(1R)-1-(甲氧基羰基)乙基]-β-D-吡喃葡萄糖基氧基)-3-苯甲酰氧基-4-十八碳烯(7)，其被转化为(2S,3R,4E)-1-(2-脱氧-2-十六烷酰氨基-3-O-[(2R)-丙酰基-(L-丙氨酰-D-异谷氨酰胺苄酯)-2-基]-β-D-吡喃葡萄糖基氧基)-2-十六烷酰氨基-4-十八碳烯-醇(14)。3α与叔丁基二甲基甲硅烷基2-叠氮基-3,6-二-O-苄基-2-脱氧-β-D-吡喃葡萄糖苷(15)反应得到叔丁基二甲基甲硅烷基2-叠氮基-4-O-(2-叠氮基-2-脱氧-4,6-O-异亚丙基-3-O-[(1R)-1-(甲氧基羰基)乙基]-β-D-吡喃葡萄糖基)-3,6-二-O-苄基-2-脱氧-β-D-吡喃葡萄糖苷(16β)，其被转化为1,3,6-三-O-乙酰基-2-脱氧-4-O-(4,6-二-O-乙酰基-2-脱氧-2-十六烷酰氨基-3-O-[2R)-丙酰基-(L-丙氨酰-D-异谷氨酰胺甲酯)-2-基]-β-D-吡喃葡萄糖基)-2-十六烷酰氨基-D-吡喃葡萄糖(27)。
