Lehmann J, Ziser L
Institut für Organische Chemie und Biochemie, Universität Freiburg, F.R.G.
Carbohydr Res. 1990 Sep 19;205:93-103. doi: 10.1016/0008-6215(90)80131-l.
O-Deacylation and S-deacylation of the diastereomers of 2-azido-4-S-benzoyl-4-mercaptobutyl 2,3,4,6-tetra-O-acetyl-alpha-D-glucopyranoside (9) with methanolic sodium methoxide and coupling of the resulting thiol to methyl 3,4-anhydro-6-deoxy-beta-L-arabino-hex-5-enopyranoside (2) gave the corresponding diastereomers of the spacer-modified disaccharide methyl 4-S-(3-azido-4-alpha-D-glucopyranosyloxybutyl)-6-deoxy-4-thio-alph a-D-xylo-hex-5-enopyranoside (10). Glucosylation of the diastereomers of 10 with alpha-cyclo-dextrin-CGTase and treatment of the products with beta-amylase gave the diastereomers of the spacer-modified oligosaccharides methyl 4-S-(3-azido-4-alpha-maltosyloxybutyl)-6-deoxy-4-thio-alpha-D-xylo -hex-5-enopyranosides (11) and 4-S-(3-azido-4-alpha-maltotriosyloxybutyl)-6-deoxy-4-thio-alpha-D- hex-5-enopyranosides (12). The diastereomers of 10 each had a good affinity for pancreatic alpha-amylase and the maltose-binding protein from E. coli. The affinities of the diastereomers of 11 and 12 were higher by at least one order of magnitude.
用甲醇钠对2-叠氮基-4-S-苯甲酰基-4-巯基丁基2,3,4,6-四-O-乙酰基-α-D-吡喃葡萄糖苷（9）的非对映异构体进行O-脱酰基化和S-脱酰基化反应，并将所得硫醇与3,4-脱水-6-脱氧-β-L-阿拉伯-己-5-烯吡喃糖苷（2）偶联，得到间隔基修饰的二糖甲基4-S-(3-叠氮基-4-α-D-吡喃葡萄糖氧基丁基)-6-脱氧-4-硫代-α-D-木糖-己-5-烯吡喃糖苷（10）的相应非对映异构体。用α-环糊精-CGTase对10的非对映异构体进行糖基化反应，并用β-淀粉酶处理产物，得到间隔基修饰的寡糖甲基4-S-(3-叠氮基-4-α-麦芽糖氧基丁基)-6-脱氧-4-硫代-α-D-木糖-己-5-烯吡喃糖苷（11）和4-S-(3-叠氮基-4-α-麦芽三糖氧基丁基)-6-脱氧-4-硫代-α-D-己-5-烯吡喃糖苷（12）的非对映异构体。10的非对映异构体对胰α-淀粉酶和来自大肠杆菌的麦芽糖结合蛋白均具有良好的亲和力。11和12的非对映异构体的亲和力至少高一个数量级。
