p-tolyl 2,6-di-O-benzyl-1-thio-β-D-galactopyranoside | 200406-60-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: p-tolyl 2,6-di-O-benzyl-1-thio-β-D-galactopyranoside
• 英文别名: (2R,3R,4S,5R,6S)-6-(4-methylphenyl)sulfanyl-5-phenylmethoxy-2-(phenylmethoxymethyl)oxane-3,4-diol
• CAS: 200406-60-6
• 化学式: C₂₇H₃₀O₅S
• 分子量: 466.598
• InChiKey: KTFZDMWVDNUVKT-KQZFZZGISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  33
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  93.4
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  p-tolyl 2,6-di-O-benzyl-1-thio-β-D-galactopyranoside 在 吡啶 、 甲醇 、 N-碘代丁二酰亚胺 、 sodium methylate 作用下， 以 二氯甲烷 为溶剂， 反应 2.58h， 生成 p-methoxyphenyl 2,6-di-O-benzyl-α-D-galactopyranosyl-(1→3)-4,6-O-benzylidene-2-deoxy-2-phthalimido-β-D-glucopyranoside
  参考文献：
  名称：

  Chemical Synthesis of the Pentasaccharide Related to the Repeating Unit of theO-Antigen fromSalmonella entericaO4

  摘要：

  GRAPHICAL ABSTRACT[GRAPHICS]Concise chemical synthesis of the pentasaccharide repeating unit of the O-antigen from Salmonella enteric O44 in the form of its p-methoxyphenyl glycoside is reported. The synthesis is accomplished by using rationally protected monosaccharide building blocks prepared from commercially available D-Glc, D-GlcNH(2).HCl, and D-Gal. Phthalimido groups were used as the precursor of the required acetamido groups for successful 1,2-trans glycosylations. Stereoselective glycosylations are achieved either through activation of thioglycosides using NIS and H2SO4-silica or through activation of trichloroacetimidate using H2SO4-silica alone.

  DOI：

  10.1080/07328303.2015.1047503

文献信息

• Low-Concentration 1,2-<i>trans</i>β-Selective Glycosylation Strategy and Its Applications in Oligosaccharide Synthesis
  作者：Chin-Sheng Chao、Chen-Wei Li、Min-Chun Chen、Shih-Sheng Chang、Kwok-Kong Tony Mong

  DOI：10.1002/chem.200901119

  日期：2009.10.19

  This study develops an operationally easy, efficient, and general 1,2‐trans β‐selective glycosylation reaction that proceeds in the absence of a C2 acyl function. This process employs chemically stable thioglycosyl donors and low substrate concentrations to achieve excellent β‐selectivities in glycosylation reactions. This method is widely applicable to a range of glycosyl substrates irrespective of

  这项研究开发了一种易于操作，有效且通用的1,2-反式β-选择性糖基化反应，该反应在没有C2酰基功能的情况下进行。该过程采用化学上稳定的硫糖基供体和低底物浓度，以在糖基化反应中实现出色的β选择性。该方法可广泛应用于各种糖基底物，无论其结构和羟基保护功能如何。碳水化合物化学中这种低浓度的1,2-反式β-选择性糖基化消除了使用高反应性硫糖苷构建1,2-反式的限制β糖苷键。这有利于寡糖合成新策略的设计，如生物学相关的β-（1→6）-葡聚糖三糖，β-连接的Gb 3和isoGb 3衍生物的制备所示。
• Regioselective Acylation of Diols and Triols: The Cyanide Effect
  作者：Peng Peng、Michael Linseis、Rainer F. Winter、Richard R. Schmidt

  DOI：10.1021/jacs.6b02454

  日期：2016.5.11

  positioned hydroxy groups. As cyanide is capable of various kinds of hydrogen bonding and as it is a quite strong sterically nondemanding base, regioselective O-acylations should be possible at low temperatures even at sterically congested positions, thus permitting formation and also isolation of the kinetic product. Indeed, 1,2-cis-diols, having an equatorial and an axial hydroxy group, benzoyl cyanide

  碳水化合物化学的中心主题包括碳水化合物的结构修饰和寡糖合成。两者都需要受区域选择性保护的构建块，这些构建块主要通过间接多步程序获得。因此，需要针对特定​​羟基的直接保护方法。双氢键最终将区分不同位置的羟基。由于氰化物能够形成各种氢键，并且它是一种非常强的空间要求不高的碱，因此即使在空间拥挤的位置，也应该可以在低温下进行区域选择性 O-酰化，从而允许形成和分离动力学产物。实际上，具有赤道和轴羟基的 1,2-顺式二醇、苯甲酰氰或乙酰氰作为酰化剂，和 DMAP 作为催化剂在 -78°C 下产率热力学上不利的轴向 O-酰化产物；在这些条件下未观察到酰基迁移。这种现象被 3,4-O-未保护的半乳糖和吡喃岩藻糖苷以及 2,3-O-未保护的吡喃甘露糖苷证实。即使对于作为三醇的 3,4,6-O-未保护的吡喃半乳糖苷，轴向 4-O-酰化也明显快于伯 6-羟基的 O-酰化。氢键对这种不寻常的区域选择性的重要性可以通过
• One-Pot Regioselective Diacylation of Pyranoside 1,2-<i>cis</i> Diols
  作者：Taeok Kim、Michael R. Bell、V. Narasimharao Thota、Todd L. Lowary

  DOI：10.1021/acs.joc.2c00252

  日期：2022.4.1

  A one-pot strategy for functionalizing pyranoside 1,2-cis-diols with two different ester protecting groups is reported. The approach employs regioselective acylation via orthoester hydrolysis promoted by a carboxylic acid, e.g., levulinic acid, acetic acid, benzoic acid, or chloroacetic acid. Upon removal of water and introduction of a coupling agent, the carboxylic acid is esterified to the hydroxyl

  报道了一种用两种不同的酯保护基团对吡喃糖苷 1,2-顺式二醇进行功能化的一锅法。该方法通过由羧酸例如乙酰丙酸、乙酸、苯甲酸或氯乙酸促进的原酸酯水解使用区域选择性酰化。在除去水并引入偶联剂后，羧酸酯化为水解过程中释放的羟基。虽然适用于吡喃糖苷支架上的 1,2-顺式二醇，但该方法应适用于任何六元环上的此类基序。
• Pre-activation based, highly alpha-selective O-sialylation with N-acetyl-5-N,4-O-carbonyl-protected p-tolyl thiosialoside donor
  作者：Bin Sun、Heyan Jiang

  DOI：10.1016/j.tetlet.2011.09.022

  日期：2011.11

  A new method for pre-activation of N-acetyl-5-N,4-O-carbonyl-protected p-tolyl thiosialoside donor with AgOTf and p-toluenesulfenyl chloride followed by coupling with other p-tolyl thioglycosides is reported. Excellent alpha-sialylation yields were achieved for these coupling reactions, as high as 91% yield of only alpha-isomer. (C) 2011 Elsevier Ltd. All rights reserved.