ethyl 3,4,6-tri-O-acetyl-2-azido-2-deoxy-1-thio-α-D-glucopyranoside | 1043887-04-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 3,4,6-tri-O-acetyl-2-azido-2-deoxy-1-thio-α-D-glucopyranoside
• 英文别名: thioethyl 3,4,6-O-acetyl-2-azido-2-deoxy-α-D-glucopyranoside
• CAS: 1043887-04-2
• 化学式: C₁₄H₂₁N₃O₇S
• 分子量: 375.403
• InChiKey: IMXKEJXTNCXKBL-DHGKCCLASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.57
• 重原子数：
  25.0
• 可旋转键数：
  7.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  136.89
• 氢给体数：
  0.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  ethyl 3,4,6-tri-O-acetyl-2-azido-2-deoxy-1-thio-α-D-glucopyranoside 在 palladium on activated charcoal 2,6-二叔丁基-4-甲基吡啶 、 4 A molecular sieve 、 氢气 、 DMTST 作用下， 以 乙醇 、 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 22.42h， 生成 [(2R,3S,4R,5R,6S)-5-acetamido-3,4-diacetyloxy-6-[(2R,3S,4R,5S,6S)-4,5-diacetamido-2-(hydroxymethyl)-6-[2-[4-[(2,2,2-trifluoroacetyl)amino]phenyl]ethoxy]oxan-3-yl]oxyoxan-2-yl]methyl acetate
  参考文献：
  名称：

  百日咳博德特氏菌脂多糖含间隔基二糖片段的合成。

  摘要：

  2-O-（2-乙酰氨基-2-脱氧-α-D-吡喃葡萄糖基）-2,3-二乙酰氨基-2,3-二脱氧-α-D-甘露吡喃糖苷二糖2-（对氨基苯基）乙基假定这是百日咳博德特氏菌多糖的部分结构，分别从D-葡萄糖和D-葡萄糖胺开始合成。主要的合成转化是D-氨基葡萄糖转化为供体3,4,6-三-O-乙酰基-2-叠氮基-2-脱氧-1-硫代-硫代-β-D-吡喃葡萄糖苷和葡萄糖的转化序列涉及2,3-环氧化合物的形成/开放，在3位上的亲核三氟甲磺酸酯置换以及必要的保护基操纵，进入受体2-（对-三氟乙酰氨基苯基）乙基6-O-苄基-2,3-二叠氮基2 ，3-二脱氧-α-D-甘露吡喃糖苷。

  DOI：

  10.1016/s0008-6215(99)00318-3
• 作为产物：
  描述：

  (乙基硫代)三甲基硅烷 、 2-叠氮基-2-脱氧-D-吡喃葡萄糖1,3,4,6-四乙酸酯 在 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 反应 20.0h， 以9.92 g的产率得到ethyl 3,4,6-tri-O-acetyl-2-azido-2-deoxy-1-thio-α-D-glucopyranoside
  参考文献：
  名称：

  Solid-Phase Synthesis of α-Glucosamine Sulfoforms with Fragmentation Analysis by Tandem Mass Spectrometry

  摘要：

  Sulfated epitopes of alpha-glucosamine (GlcN sulfoforms) were prepared by solid-phase synthesis as models of internal glucosamines within heparan sulfate. An orthogonally protected 2'-hydroxyethyl GlcN derivative was immobilized on a trityl resin support and subjected to regioselective deprotection and sulfonation conditions, which were optimized with the aid of on-resin infrared or Raman analysis. The sulfoforms were cleaved from the resin under mild Lewis acid conditions without affecting the O- or N-sulfate groups and purified by reversed-phase high-performance liquid chromatography (HPLC). The alpha-GlcN sulfoforms and their 4-O-benzyl ethers were examined by electrospray ionization tandem mass spectrometry (ESI-MS/MS), with product ion spectra produced by collision-induced dissociation (CID). ESI-MS/MS revealed significant differences in parent ion stabilities and fragmentation rates as a function of sulfate position. Ion fragmentation by CID resulted in characteristic mass losses with strong correlation to the positions of both free hydroxyl groups and sulfate ions. Most of these fragmentation patterns are consonant with elimination pathways, and suggest possible strategies for elucidating the structures of glucosamine-derived sulfoforms with identical m/z ratios. In particular, fragmentation analysis can easily distinguish GlcN sulfoforms bearing the relatively rare 3-O-sulfate from isomers with the more common 6-O-sulfate.

  DOI：

  10.1021/jo800713m

文献信息

• Lipid A Mimetics Based on Unnatural Disaccharide Scaffold as Potent TLR4 Agonists for Prospective Immunotherapeutics and Adjuvants
  作者：Sebastian Strobl、Karin Hofbauer、Holger Heine、Alla Zamyatina

  DOI：10.1002/chem.202200547

  日期：2022.6.21

  human diseases, the development of novel TLR4 activating biomolecules other than lipid A is of vast importance. We report on design, chemical synthesis and immunobiology of novel glycan-based lipid A-mimicking molecules that can activate human and murine TLR4-mediated signaling with picomolar affinity. Exploiting crystal structure - based design we have created novel disaccharide lipid A mimetics (DLAMs)

  TLR4是一种关键的模式识别受体，可以感知病原体和危险相关的分子模式，从而激活下游信号通路，从而导致转录因子上调以及干扰素和细胞因子的表达，从而介导参与免疫防御的保护性促炎反应。细菌脂质 A 是主要的 TLR4 配体，具有非常复杂、物种特异性且难以预测的构效关系。鉴于 TLR4 的治疗靶向是治疗多种人类疾病的新兴工具，因此开发除脂质 A 之外的新型 TLR4 激活生物分子非常重要。我们报告了新型基于聚糖的脂质 A 模拟分子的设计、化学合成和免疫生物学，该分子可以以皮摩尔亲和力激活人和小鼠 TLR4 介导的信号传导。利用基于晶体结构的设计，我们创建了新型二糖脂质 A 模拟物 (DLAM)，其中脂质 A 固有的柔性 β(1→6) 连接的二葡萄糖胺主链与构象限制的非还原性 βGlcN(1↔1') 进行交换βGlcN 支架。通过使用保护基操作策略调整供体和受体分子的反应性，在具有挑战性的 β,β-1