| 181584-01-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• CAS: 181584-01-0
• 化学式: C₁₉H₁₇Cl₇N₂O₇
• 分子量: 633.524
• InChiKey: CLNQQSIYQANETB-ICLPOSBMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  35.0
• 可旋转键数：
  5.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  116.17
• 氢给体数：
  2.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  在 吡啶 、 三氟甲磺酸三甲基硅酯 、 4 A molecular sieve 、 硫脲 作用下， 以 乙醇 为溶剂， 反应 21.0h， 生成 (2S,3S,4S,5R,6R)-4,5-Bis-benzoyloxy-3-[(2R,4aR,6S,7R,8R,8aS)-8-hydroxy-2-phenyl-7-(2,2,2-trichloro-acetylamino)-hexahydro-pyrano[3,2-d][1,3]dioxin-6-yloxy]-6-methoxy-tetrahydro-pyran-2-carboxylic acid methyl ester
  参考文献：
  名称：

  The use of 2-deoxy-2-trichloroacetamido-?-glucopyranose derivatives in syntheses of hyaluronic acid-related tetra-, hexa-, and octa-saccharides having a methyl β-?-glucopyranosiduronic acid at the reducing end

  摘要：

  DOI：

  10.1016/0008-6215(96)00085-7
• 作为产物：
  描述：

  三氯乙腈 、 在 silica gel 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 生成 、 2,2,2-Trichloro-acetimidic acid (2R,4aR,6R,7R,8R,8aS)-2-phenyl-6-(2,2,2-trichloro-acetimidoyloxy)-7-(2,2,2-trichloro-acetylamino)-hexahydro-pyrano[3,2-d][1,3]dioxin-8-yl ester
  参考文献：
  名称：

  The use of 2-deoxy-2-trichloroacetamido-?-glucopyranose derivatives in syntheses of hyaluronic acid-related tetra-, hexa-, and octa-saccharides having a methyl β-?-glucopyranosiduronic acid at the reducing end

  摘要：

  DOI：

  10.1016/0008-6215(96)00085-7

文献信息

• Convergent synthesis of tetra- and penta-saccharide fragments of dimeric Lewis X
  作者：Adam Forman、Jenifer Hendel、France-Isabelle Auzanneau

  DOI：10.1016/j.carres.2019.06.009

  日期：2019.8

  The convergent synthesis of tetra- and penta-saccharide fragments of the TACA dimeric Lex is described. The synthetic strategy relied on the preparation of a protected GlcNTCA-(1,3)-Gal-(1,4)-GlcNAc trisaccharide diol free at O-3 of both glucosamine residues. Key steps in the preparation of this diol involved glycosylation at O-4 of N-acetylglucosamine using activation of a trichloroacetimidate with

  描述了TACA二聚体Lex的四糖和五糖片段的收敛合成。合成策略依赖于制备两个葡糖胺残基的O-3均不含的受保护的GlcNTCA-（1,3）-Gal-（1,4）-GlcNAc三糖二醇。制备该二醇的关键步骤包括在40°C下用BF3·Et2O活化三氯乙酰亚氨酸酯在N-乙酰氨基葡糖的O-4处进行糖基化，用硫脲除去非还原性O-3'氯乙酸末和糖基化。 N-三氯乙酰胺基氨基葡萄糖三氯乙酰亚胺酸酯供体。转化为二醇受体后，三糖在NIS / TMSOTf激活下的非还原端被选择性地岩藻糖基化，或在CuBr2 / Bu4NBr激活下被二岩藻糖基化。然后在溶解的金属条件下将被保护的四糖和五糖有效地脱保护，并且在反应后处理中非还原性末端葡糖胺残基被N-乙酰化。脱保护的化合物将用作可溶性竞争剂，以表征被抗聚合Lex抗体识别的表位。
• Synthesis of Tumor-Associated Le^aLe^x Hexasaccharides: Instability of a Thiol-Containing Oligosaccharide in Mass Spectrometry and Hypermetalation Detected by ESI FAIMS
  作者：Mickaël Guillemineau、Jadwiga Lyczko、Wojciech Gabryelski、France-Isabelle Auzanneau

  DOI：10.1021/acs.joc.5b01190

  日期：2015.8.21

  We report the efficient synthesis of three analogues of the tumor-associated carbohydrate antigen LeaLex. This hexasaccharide was prepared as a soluble inhibitor hexyl glycoside, as a 6-aminohexyl glycoside for conjugation to proteins, and as a 6-thiohexyl glycoside for immobilization to a gold surface. These three analogues were obtained from a common hexasaccharide intermediate and isolated pure

  我们报告了肿瘤相关的碳水化合物抗原Le a Le x的三个类似物的有效合成。该六糖被制备为可溶性抑制剂己基糖苷，用于与蛋白质缀合的6-氨基己基糖苷和用于固定至金表面的6-硫己基糖苷。这三种类似物是从一种常见的六糖中间体中分离得到的，然后经过涉及金属溶解条件的有效脱保护反应而分离得到。尽管所有其他中间体和类似物在ESI HRMS中均提供了预期的分子离子，但6-硫代己基糖苷的最终化合物给出了一个复杂的光谱，其中没有信号与该分子离子相匹配。使用ESI FAIMS HRMS，我们能够防止离子解离反应并获得高质量的光谱数据。所检测到的离子可以通过其准确质量进行明确表征，从而洞悉了硫己基类似物在气相中的行为。
• Convergent Preparation of DimLex Hexasaccharide Analogues
  作者：Jenifer L. Hendel、France-Isabelle Auzanneau

  DOI：10.1002/ejoc.201101342

  日期：2011.12

  O-3 of the reducing end glucosamine units led to some loss of the fucosyl units already introduced at O-3 of the nonreducing end glucosamine residues. Despite this hurdle, optimization of the glycosylation conditions provided the desired hexasaccharides in sufficient quantities to prepare the final analogues. Propyl glycosides and cysteamine adducts were prepared easily in two steps from the protected

  我们报告了四种六糖的聚合制备，用于合成基于肿瘤相关碳水化合物抗原 dimLex 的安全抗癌疫苗。一种常见的三糖中间体首先被合成为四糖骨架的前体。然后将这些四糖转化为二醇受体并在两个葡糖胺残基的 O-3 处进行岩藻糖基化。促进还原性末端葡糖胺单元的 O-3 处的岩藻糖基化所需的条件导致已经在非还原性末端葡糖胺残基的 O-3 处引入的岩藻糖基单元的一些损失。尽管有这个障碍，糖基化条件的优化提供了足够数量的所需六糖来制备最终的类似物。
• Synthesis of Dimeric Lewis A and Lewis B–Lewis A Tumor-Associated Carbohydrate Antigen Oligosaccharide Fragments
  作者：Jeffrey Davidson、Charles Gauthier-Signore、France-Isabelle Auzanneau

  DOI：10.1021/acs.joc.3c00082

  日期：2023.5.5

  immunotherapies, little research has been conducted on these antigens. In our quest to discover fragments of these TACAs that could be targeted for the development of anticancer therapeutics, we report the synthesis of eight tri- to pentasaccharide fragments of these oligosaccharides. Unforeseen synthetic challenges are reported such as the incompatibility of a bromoalkyl glycoside in the reduction conditions

  尽管肿瘤相关碳水化合物抗原（TACA）dimLe a和Le b Le a具有令人感兴趣的潜力为了开发抗癌免疫疗法，对这些抗原进行的研究很少。在我们寻找可用于开发抗癌疗法的 TACA 片段的过程中，我们报告了这些寡糖的八个三糖至五糖片段的合成。报告了不可预见的合成挑战，例如溴烷基糖苷在还原三氯乙酰胺所需的还原条件下的不相容性、2 + 1 合成策略中的反应性不匹配，以及 C-4 GlcNAc 羟基与 C-4 GlcNAc 羟基的令人惊讶的更高反应性三糖二醇选择性糖基化中的半乳糖基 OH-3。在溶解金属条件下进行一步脱保护反应后，最终以壬基或9-氨基壬基糖苷的形式获得所需的最终化合物。9-氨基壬基糖苷将与载体蛋白缀合，壬基五糖苷将在结合实验中用作可溶性抑制剂。相比之下，壬基四糖苷难溶于水，其在生化实验中的应用受到限制。
• Aggregation of a Tetrasaccharide Acceptor Observed by NMR: Synthesis of Pentasaccharide Fragments of the Le^aLe^x Tumor-Associated Hexasaccharide Antigen
  作者：Deng Kuir、Mickaël Guillemineau、France-Isabelle Auzanneau

  DOI：10.1021/acs.joc.5b00405

  日期：2015.5.15

  We report the synthesis of a tetrasaccharide and two pentasaccharide fragments of the Le(a)Le(x) tumor-associated carbohydrate antigen alpha-L-Fuc-(1 -> 4)-[beta-d-Gal-(1 -> 3)]-beta-d-GlcNAc-(1 -> 3)-beta-d-Gal-(1 -> 4)-[alpha-l-Fuc-(1 -> 3)]-beta-d-GlcNAc-(1 -> OR). The choice of protecting groups permitted a one-step global deprotection (Na/NH3(l)). The protected chlorohexyl glycoside pentasaccharide was the precursor to the hexyl glycoside, to be used as a soluble inhibitor, and the aminohexyl glycoside analogue, to be conjugated to proteins for surface immobilization and immunization experiments. We observed that a linear tetrasaccharide that contained two N-acetylglucosamine residues and a free OH group gave two distinct sets of H-1 NMR signals when the data were acquired in deuterated chloroform. Data acquisition at variable concentrations and variable temperatures suggests that the second set of NMR signals results from aggregation of the tetrasaccharide driven by the formation of intermolecular H-bonds involving the NHAc. While the formation of intra- and intermolecular H-bonds involving N-acetylgucosamine residues has been reported in non-H-bonding solvents, this is, to our knowledge, the first time that these have lead to the appearance of two distinct sets of signals in the NMR spectra. This aggregation may explain the lack of reactivity observed when an attempt is made to glycosylate such an acceptor using non-H-bonding solvents such as dichloromethane.