p-tolyl-3,4,6-tri-O-benzyl-1-thio-α-D-mannopyranoside | 793672-50-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: p-tolyl-3,4,6-tri-O-benzyl-1-thio-α-D-mannopyranoside
• 英文别名: 4-methylphenyl 3,4,6-tri-O-benzyl-1-thio-α-D-mannopyranoside；tolyl 3,4,6-tri-O-benzyl-α-D-thiomannopyranoside；p-methylphenyl 3,4,6-tri-O-benzyl-1-thio-α-D-mannopyranoside；p-tolyl-3,4,5-tri-O-benzyl-1-thio-α-D-mannopyranoside；(2R,3S,4R,5R,6R)-2-(4-methylphenyl)sulfanyl-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-3-ol
• CAS: 793672-50-1
• 化学式: C₃₄H₃₆O₅S
• 分子量: 556.723
• InChiKey: FADNYQJXIQUXGW-KKYNAJBLSA-N

物化性质

• 沸点：
  698.5±55.0 °C(Predicted)
• 密度：
  1.23±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  40
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  82.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  p-tolyl-3,4,6-tri-O-benzyl-1-thio-α-D-mannopyranoside 在 bis(1,5-cyclooctadiene)diiridium(I) dichloride 2,6-二叔丁基-4-甲基吡啶 、 碘 、 silver trifluoromethanesulfonate 、 sodium carbonate 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 62.0h， 生成 4-methylphenyl 3,4,6-tri-O-benzyl-2-O-(2-iodo-1-(methyl 2-O-benzyl-4,6-O-benzylidene-α-D-mannopyranos-3-O-yl)ethyl)-1-thio-α-D-mannopyranoside
  参考文献：
  名称：

  Stereospecific Synthesis of 1,2-cis Glycosides by Vinyl-Mediated IAD

  摘要：

  (GRAPHICS)Stereospecific 1,2-cis glycosylation of 2-O-vinyl thioglycosides, synthesized from the corresponding alcohols by Ir-catalyzed transvinylation with vinyl acetate, is achieved by iodine-mediated tethering of a range of primary and secondary carbohydrate acceptors, followed by intramolecular aglycon delivery (IAD). The use of such an intramolecular glycosylation strategy furnishes the desired alpha-gluco and beta-manno disaccharides in an entirely stereoselective manner.

  DOI：

  10.1021/ol048427o
• 作为产物：
  描述：

  3,4,6-tri-O-acetyl-1,2-O-(1-methoxyethylidene)-β-D-mannopyranose 在 甲醇 、 三氟化硼乙醚 、 sodium 作用下， 以 二氯甲烷 为溶剂， 生成 p-tolyl-3,4,6-tri-O-benzyl-1-thio-α-D-mannopyranoside
  参考文献：
  名称：

  C-2醚功能在丁腈溶剂指导的糖基化反应中的相邻基团参与

  摘要：

  当在腈溶剂混合物中进行反应时，已发现在C-2羟基处的醚保护功能在糖基化中起参与作用。参与机制基于C-2醚功能的氧原子的孤电子对和腈分子以顺式排列时的分子内相互作用。形成一个1,2-顺式糖基恶唑啉鎓中间体。这种参与，再加上糖基供体的异头作用，赋予糖基化较高的1,2-反式选择性。该概念的进一步应用导致了α-（1→5）-阿拉伯低聚物的高效制备。

  DOI：

  10.1002/chem.201100732

文献信息

• A Concise Synthesis of Oligosaccharides Derived From Lipoarabinomannan (LAM) with Glycosyl Donors Having a Nonparticipating Group at C2
  作者：Zhihao Li、Changping Zheng、Marco Terreni、Teodora Bavaro、Matthieu Sollogoub、Yongmin Zhang

  DOI：10.1002/ejoc.201901915

  日期：2020.4.16

  is one of the top ten leading causes of death over the world, and lipoarabinomannan (LAM) has been confirmed to play significant roles in this process. In this study, a convenient synthetic approach has been developed for the synthesis of oligosaccharides derived from LAM starting with commercially available substrates and reagents. The key steps for stereoselective construction of glycosidic bonds by

  导致结核病 (TB) 的分枝杆菌感染是全球十大主要死亡原因之一，而脂阿拉伯甘露聚糖 (LAM) 已被证实在此过程中发挥着重要作用。在这项研究中，开发了一种方便的合成方法，用于从市售底物和试剂开始合成源自 LAM 的寡糖。实现了在没有相邻参与组的情况下通过与供体糖基化的受体立体选择性构建糖苷键的关键步骤。值得注意的是，采用酶水解制备甘露糖结构单元，并采用桦木反应一步法脱去乙酰基和苄基以及还原叠氮基，避免了多次化学过程。最后，
• Synthesis of Mannosidase-Stable Man₃ and Man₄ Glycans Containing S-linked Manα1→2Man Termini
  作者：Mahesh Neralkar、Leiming Tian、Richard L. Redman、Isaac J. Krauss

  DOI：10.1021/acs.orglett.1c00726

  日期：2021.4.16

  of interest as HIV vaccine components, but they are subject to mannosidase degradation in vivo. Herein, we report the synthesis of oligosaccharides containing a thio linkage at the nonreducing end. A thio-linked dimannose donor participates in highly stereoselective glycosylations to afford trimannose and tetramannose fragments. Saturation transfer difference nuclear magnetic resonance (STD NMR) studies

  寡甘露糖聚糖作为 HIV 疫苗成分是令人感兴趣的，但它们在体内会发生甘露糖苷酶降解。在此，我们报告了在非还原端含有硫键的寡糖的合成。硫键连接的二甘露糖供体参与高度立体选择性糖基化以提供三甘露糖和四甘露糖片段。饱和转移差异核磁共振 (STD NMR) 研究表明，这些聚糖被 HIV 抗体 2G12 识别，并且我们确认还原末端 S 键对x 具有完全的稳定性。manihotis甘露糖苷酶。
• Reversing the Stereoselectivity of a Palladium-Catalyzed O-Glycosylation through an Inner-Sphere or Outer-Sphere Pathway
  作者：Shaohua Xiang、Kim Le Mai Hoang、Jingxi He、Yu Jia Tan、Xue-Wei Liu

  DOI：10.1002/anie.201408739

  日期：2014.11.3

  An efficient and concise method for the construction of various O‐glycosidic bonds by a palladium‐catalyzed reaction with a 3‐O‐picoloyl glucal has been developed. The stereochemistry of the anomeric center derives from either an inner‐sphere or outer‐sphere pathway. Harder nucleophiles, such as aliphatic alcohols and sodium phenoxides give β‐products, and α products result from using softer nucleophiles

  已开发出一种高效，简捷的方法，可通过钯与3-O-吡啶甲酸葡糖的催化反应来构建各种O-糖苷键。异头中心的立体化学来自内球或外球途径。较硬的亲核试剂（例如脂族醇和酚钠）会产生β产物，而使用较软的亲核试剂（例如苯酚）会产生α产物。
• In situ formation of β-glycosyl imidinium triflate from participating thioglycosyl donors: elaboration to disarmed–armed iterative glycosylation
  作者：Yu Hsien Lin、Bhaswati Ghosh、Kwok-Kong Tony Mong

  DOI：10.1039/c2cc35032g

  日期：——

  β-Glycosyl imidinium triflate is generated from participating thioglycoside donors for disarmed–armed iterative glycosylations and one-pot oligosaccharide synthesis.

  β-葡糖基亚胺三氟甲磺酸盐是从参与去甲基化-甲基化迭代糖基化反应的硫代糖供体中生成的，并用于一步法寡糖合成。
• β-Type Glycosidic Bond Formation by Palladium-Catalyzed Decarboxylative Allylation
  作者：Shaohua Xiang、Zhiqiang Lu、Jingxi He、Kim Le MaiHoang、Jing Zeng、Xue-Wei Liu

  DOI：10.1002/chem.201303241

  日期：2013.10.11

  Decarboxylative allylation of glycals: A β‐type glycosidic bond has been constructed in high regio‐ and stereoselectivity by means of a palladium‐catalyzed decarboxylative O‐glycosylation. Various kinds of glycals with different protecting groups have been examined for this reaction to afford a diverse set of glycosylated products, including phenolic O‐glycosides, thiophenolic S‐glycoside, aliphatic

  糖类的脱羧烯丙基化：通过钯催化的脱羧O糖基化，以高区域和立体选择性构建了β型糖苷键。已对该反应进行了各种具有不同保护基的糖基的检测，以提供各种糖基化产物，包括酚O-糖苷，硫酚S-糖苷，脂族O-糖苷和具有出色的β-选择性和合理至优异的二糖。产量（请参阅计划）。