3,4-O-isopropylidene-6-O-(1-methoxy-1-methylethyl)-1-thio-β-D-galactopyranoside | 270075-72-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,4-O-isopropylidene-6-O-(1-methoxy-1-methylethyl)-1-thio-β-D-galactopyranoside
• 英文别名: phenyl 3,4-O-isopropylidene-6-O-(2-methoxy-2-methylethyl)-1-thio-β-D-galactopyranoside；phenyl 1-thio-3,4-O-isopropylidene-6-O-(1-methoxyl-1-methylethyl)-β-D-galactopyranoside；(3aS,4R,6S,7R,7aR)-4-(2-methoxypropan-2-yloxymethyl)-2,2-dimethyl-6-phenylsulfanyl-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-7-ol
• CAS: 270075-72-4
• 化学式: C₁₉H₂₈O₆S
• 分子量: 384.494
• InChiKey: OBQXYTGKQBGXOQ-UUAJXVIYSA-N

物化性质

• 沸点：
  511.1±50.0 °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)：
  2.4
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  91.7
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  3,4-O-isopropylidene-6-O-(1-methoxy-1-methylethyl)-1-thio-β-D-galactopyranoside 在 4-二甲氨基吡啶 、 溶剂黄146 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 8.0h， 生成
  参考文献：
  名称：

  Mechanistic Studies and Methods To Prevent Aglycon Transfer of Thioglycosides

  摘要：

  Thioglycosides have been employed extensively for the synthesis of complex oligosaccharides, carbohydrate libraries, and mimetics of O-glycosides. While very useful, aglycon transfer is a problematic side reaction with thioglycosides. In this paper, a series of mechanistic studies are described. The aglycon transfer process is shown to affect both armed and disarmed thioglycosides, cause anomerization of the carbon-sulfur bond of a thioglycoside, and destroy the product of a glycosylation reaction. The results indicate that the aglycon transfer process can be a major problem for a wide range of thioglycosides. This side reaction is especially important to consider when carrying out complex reactions such as solid-phase glycosylations, one-pot or orthogonal multicomponent glycosylations, and construction of carbohydrate libraries. To prevent transfer, a number of modified aglycons were examined. The 2,6-dimethylphenyl ( DMP) aglycon was found to effectively block transfer in a variety of model studies and glycosylation reactions. The DMP group can be installed in one step from a commercially available thiol ( 2,6-dimethylthiophenol) and is useable as a glycosyl donor. On the basis of these features, the DMP group is proposed as a convenient and improved aglycon for thioglycosides.

  DOI：

  10.1021/ja063247q
• 作为产物：
  描述：

  beta-D-半乳糖五乙酸酯 在 camphor-10-sulfonic acid 、 sodium methylate 、 四氯化锡 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 6.0h， 生成 3,4-O-isopropylidene-6-O-(1-methoxy-1-methylethyl)-1-thio-β-D-galactopyranoside
  参考文献：
  名称：

  Mechanistic Studies and Methods To Prevent Aglycon Transfer of Thioglycosides

  摘要：

  Thioglycosides have been employed extensively for the synthesis of complex oligosaccharides, carbohydrate libraries, and mimetics of O-glycosides. While very useful, aglycon transfer is a problematic side reaction with thioglycosides. In this paper, a series of mechanistic studies are described. The aglycon transfer process is shown to affect both armed and disarmed thioglycosides, cause anomerization of the carbon-sulfur bond of a thioglycoside, and destroy the product of a glycosylation reaction. The results indicate that the aglycon transfer process can be a major problem for a wide range of thioglycosides. This side reaction is especially important to consider when carrying out complex reactions such as solid-phase glycosylations, one-pot or orthogonal multicomponent glycosylations, and construction of carbohydrate libraries. To prevent transfer, a number of modified aglycons were examined. The 2,6-dimethylphenyl ( DMP) aglycon was found to effectively block transfer in a variety of model studies and glycosylation reactions. The DMP group can be installed in one step from a commercially available thiol ( 2,6-dimethylthiophenol) and is useable as a glycosyl donor. On the basis of these features, the DMP group is proposed as a convenient and improved aglycon for thioglycosides.

  DOI：

  10.1021/ja063247q

文献信息

• Preparation of pyranoid glycal derivatives from phenyl thioglycosides and glycosyl phenyl sulphones
  作者：Alfonso Fernandez-Mayoralas、Alberto Marra、Michel Trumtel、Alain Veyrières、Pierre Sinaÿ

  DOI：10.1016/0008-6215(89)84061-3

  日期：1989.6

  quantitatively by oxidation of the corresponding phenyl thioglycosides with catalytic amounts of ruthenium trichloride in the presence of sodium periodate in a biphasic solvent system. These compounds also gave rise to pyranoid glycal derivatives in excellent yields when treated with lithium naphthalenide in tetrahydrofuran at low temperature. A β-linked 2′-deoxydisaccharide glycal derivative was also

  摘要具有萘基的锂在室温下于四氢呋喃中处理后，带有各种保护基（缩醛，醚，酯）的苯硫基吡喃葡萄糖吡喃糖类在C-1处进行还原锂化，然后快速去除2-取代基。因此，以优异的产率获得了具有酸不稳定的保护基的吡喃糖基聚糖衍生物。在双相溶剂体系中，在高碘酸钠存在下，用催化量的三氯化钌氧化相应的苯基硫代糖苷，可定量制备缩水甘油基苯基砜。当在四氢呋喃中用萘嵌锂在低温下处理时，这些化合物还以优异的产率产生吡喃类糖基衍生物。还从相应的二糖苯基硫代糖苷制备了β-连接的2'-脱氧二糖糖基衍生物。当用氢化三丁基锡处理时，带有2-黄原酸酯基团的苯基硫代吡喃糖吡喃糖苷经过自由基还原消除，从而在中性条件下以高收率得到糖基衍生物。
• A new strategy in oligosaccharide synthesis using lipophilic protecting groups: synthesis of a tetracosasaccharide
  作者：Vince Pozsgay

  DOI：10.1016/s0957-4166(99)00553-4

  日期：2000.1

  The use of lipophilic, acyl-type protecting groups in the synthesis of higher-membered oligosaccharides is described by the example of oligosaccharides corresponding to the O-specific polysaccharide (O-SP) of Shigella dysenteriae type 1. Thus, O-stearoylated and O-lauroylated l-rhamnose and d-galactose precursors, respectively, were synthesized and were combined together with a 2-azido-2-deoxy-d-glucopyranosyl

  保护基团在更高元的寡糖的合成中使用的亲脂性，酰基型的由对应于O型特异性多糖的（O-SP）的寡糖的实例描述的志贺氏痢疾杆菌型1。因此，ö -stearoylated和ö分别合成了月桂酰化的l-鼠李糖和d-半乳糖前体，并与2-叠氮基-2-脱氧-d-吡喃葡萄糖基供体结合在一起，形成了O-SP的完全保护的脂化重复单元。该模块与另一种含有常规封闭基团的四糖缩合。通过吸附到反相吸附剂上以纯净的形式分离所得的脂化八糖，该糖可以被醇类溶剂选择性地解吸。随后使用常规保护的四糖模块作为糖基供体的链延长提供了寡糖，直至和包括四糖。所提出的方法可以大大减轻与保护寡糖中间体的常规硅胶色谱纯化有关的困难，并使用比用于硅胶色谱的溶剂便宜的环保溶剂。还提出了一种新的高效方法，该方法使用三氟甲磺酸scan作为催化剂来合成碳水化合物的缩醛和环状原酸酯。
• Synthesis of three regioisomers of the pentasaccharide part of the Skp1 glycoprotein of Dictyostelium discoideum
  作者：Zoltán B. Szabó、Mihály Herczeg、Anikó Fekete、Gyula Batta、Anikó Borbás、András Lipták、Sándor Antus

  DOI：10.1016/j.tetasy.2009.02.040

  日期：2009.5

  the form of (2-trimethylsilyl)ethyl glycosides by means of 2+3 block syntheses using the disaccharide donor at the non-reducing end, and three different trisaccharide acceptors at the reducing end. Fucosylation of (2-trimethylsilyl)ethyl 3,4,6-tri-O-benzyl-β-d-galactopyranosyl-(1→3)-4,6-O-benzylidene-2-deoxy-2-NPhth-β-d-glucopyranoside with different fucosyl donors carrying an O-(2-naphthyl)methyl ether

  在盘基网柄菌中发现了Skp1糖蛋白的线性五糖部分的三种区域异构体，通过（2-三甲基甲硅烷基）乙基糖苷的形式，通过在非还原端使用二糖供体进行2 + 3嵌段合成，以及在还原端有三个不同的三糖受体。（2-三甲基硅烷基）乙基3,4,6-三-岩藻糖基ö苄基β-d吡喃半乳糖- （1→3）-4,6- Ô -亚苄基-2-脱氧-2- Ñ PHTH-β -d-吡喃葡萄糖苷与不同的岩藻糖基供体携带O在位置C2，C3或C4处作为临时保护基的-（2-萘基）甲基醚产生了被保护的核心三糖。在选择性除去（2-萘基）甲基之后，将所得的受体用α（1→6）连接的二半乳糖基供体糖基化，以产生相应的三种区域异构的五糖。将邻苯二甲酰亚胺基部分转化为N-乙酰基，然后对可还原保护基进行催化氢化，得到了游离的目标五糖，在阐明天然五糖的确切结构时，它应该能够提供帮助。
• An improved preparation of 3,4-O-isopropylidene derivatives of α- and β-d-galactopyranosides
  作者：Giorgio Catelani、Fabrizia Colonna、Alberto Marra

  DOI：10.1016/0008-6215(88)84011-4

  日期：1988.11
• Facile synthesis of biotin-labelled α-galactosylceramide as antigen for invariant natural killer T cells
  作者：Chengfeng Xia、Wenpeng Zhang、Yalong Zhang、Robert L. Woodward、Jinhua Wang、Peng G. Wang

  DOI：10.1016/j.tet.2009.06.007

  日期：2009.8

  When iNKT cells are stimulated by the CD1d presented exogenous alpha-galactosylceramide, a myriad of cytokines are released that trigger a variety of immune responses. However, the invisibility and poor aqueous Solubility of alpha-galactosylceramide during bioassays have rendered it difficult to study the aforementioned biological responses. Accordingly, a biotin-labelled alpha-galactosylceramide was prepared to facilitate detection of this antigen in the immune process. The problematic low solubility was also remedies via incorporation of a truncated acyl chain. (C) 2009 Elsevier Ltd. All rights reserved.