Ethyl 3,6-dideoxy-1-thio-β-D-xylo-hexopyranoside | 172361-41-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Ethyl 3,6-dideoxy-1-thio-β-D-xylo-hexopyranoside
• 英文别名: (2S,3R,5R,6R)-2-ethylsulfanyl-6-methyloxane-3,5-diol
• CAS: 172361-41-0
• 化学式: C₈H₁₆O₃S
• 分子量: 192.279
• InChiKey: MKWJXXZUYGYJMD-XUTVFYLZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  75
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Ethyl 3,6-dideoxy-1-thio-β-D-xylo-hexopyranoside 在 di-tert-butyl-4-methylpyridine 、 sodium hydride 、 三氟甲烷磺酸甲酯 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 2.67h， 生成 methyl 2-O-benzoyl-6-O-benzyl-4-O-(p-methoxybenzyl)-3-O-(2'-O-(p-methoxybenzyl)-4'-O-benzyl-3',6'-dideoxy-α-D-xylo-hexopyranosyl)-α-D-mannopyranoside
  参考文献：
  名称：

  三种束缚三糖的合成，以探索熵在碳水化合物-蛋白质相互作用中的作用

  摘要：

  晶体结构数据表明，支链三糖1构成了沙门氏菌血清群B抗原的完全抗原决定簇，该抗原决定簇被单克隆抗体SE155.4识别。为了表征与在结合状态下固定糖苷扭转角相关的熵成本，已经合成了该三糖2-4的三种不同的分子内束缚类似物。两个三糖通过3,6-二脱氧己糖的O-2位置通过亚甲基乙缩醛进行束缚，后者与半乳糖（2）的O- 2或甘露糖（3）的O-4相当。第三根系绳，α，α′-二硫代-p-二甲苯，跨越甘露糖和半乳糖残基的C-6原子，以创建三糖4。2和3的缩醛系链跨越了羟基中心，已知与分子内糖-糖氢键有关，但是由于不能容纳在抗体结合位点的扭曲构象，这两种三糖都没有生物学活性。三糖4是有活性的，因为半乳糖和甘露糖的羟甲基都在结合状态下暴露于溶剂，并且4的约束构象实际上与1的结合构象重叠。尽管保留了互补性并显着降低了扭转柔韧性，但三糖4个表现出Δ ģ °= -7.6千卡摩尔-1相比Δ ģ °= -7.1千卡摩尔

  DOI：

  10.1560/yxqt-2jju-ylaa-l04q
• 作为产物：
  描述：

  Ethyl 2,4-di-O-acetyl-3,6-dideoxy-1-thio-D-xylo-hexopyranoside 在 sodium methylate 作用下， 以 甲醇 为溶剂， 生成 Ethyl 3,6-dideoxy-1-thio-β-D-xylo-hexopyranoside 、 Ethyl 3,6-dideoxy-1-thio-α-D-xylo-hexopyranoside
  参考文献：
  名称：

  Synthesis of a Pentasaccharide Epitope for the Investigation of Carbohydrate-Protein Interactions

  摘要：

  Pyranose residues of a polysaccharide that are not involved in the principal sugar-protein antibody combining site, filled by trisaccharide 1, cause a 50-fold reduction in intrinsic affinity. The antibody is crystallographically characterized, and the residue responsible for the lost binding energy has been identified as the terminal disaccharide Rha-->Gal of pentasaccharide 5. This disaccharide segment of 5 may avoid protein contact by adopting the ''anti'' conformer about the preceding Man-Rha glycosidic linkage. Monosaccharide thioglycoside synthons 6-9 were used in NIS-promoted glycosylations to synthesize the pentasaccharide as a glycoside that was suitable for binding and solution conformational studies. Disaccharide 29 was obtained upon the addition of rhamnose building unit 6 to the (trimethylsilyl)ethyl galactopyranoside 10 followed by protecting group manipulation. The sequential addition of 7-9 to 29 afforded the pentasaccharide derivative 35 bearing a 2-O-benzoate group suited for subsequent 1,2-trans-glycoside synthesis following its conversion to a glycosyl imidate. In order to preserve the integrity of the 3,6-dideoxyhexopyranosyl glycosidic bond during cleavage of the (trimethylsilyl)ethyl group leading to the imidate 39, it was essential to convert the benzylated pentasaccharide target 35 into its fully acylated derivative 37. Pentasaccharide 5 was obtained by transesterification of the protected glycoside 40 formed via 39. Qualitative NOE measurements suggest a predominant solution conformation for 5 that cannot be adopted in the bound state due to protein-oligosaccharide clashes at the periphery of the binding site.

  DOI：

  10.1021/jo00127a043