phenyl 2,3,4,6-tetra-O-acetyl-1-thio-α-D-galactopyranoside | 28512-68-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: phenyl 2,3,4,6-tetra-O-acetyl-1-thio-α-D-galactopyranoside
• 英文别名: [(2R,3S,4S,5R,6R)-3,4,5-triacetyloxy-6-phenylsulfanyloxan-2-yl]methyl acetate
• CAS: 28512-68-7
• 化学式: C₂₀H₂₄O₉S
• 分子量: 440.471
• InChiKey: JCKOUAWEMPKIAT-LCWAXJCOSA-N

物化性质

• 沸点：
  514.6±50.0 °C(Predicted)
• 密度：
  1.31±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  30
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  140
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  phenyl 2,3,4,6-tetra-O-acetyl-1-thio-α-D-galactopyranoside 在 甲醇 、 sodium methylate 作用下， 反应 5.0h， 生成
  参考文献：
  名称：

  1,2-cis Alkyl glycosides: straightforward glycosylation from unprotected 1-thioglycosyl donors

  摘要：

  一个简单、直接的1,2-cis-选择性糖苷化方法，从未保护的1-硫代糖苷中呈现。

  DOI：

  10.1039/c4ob00626g
• 作为产物：
  描述：

  D-吡喃葡萄糖 在 sodium acetate 作用下， 以 二氯甲烷 为溶剂， 反应 29.5h， 生成 phenyl 2,3,4,6-tetra-O-acetyl-1-thio-α-D-galactopyranoside
  参考文献：
  名称：

  1,2-cis Alkyl glycosides: straightforward glycosylation from unprotected 1-thioglycosyl donors

  摘要：

  一个简单、直接的1,2-cis-选择性糖苷化方法，从未保护的1-硫代糖苷中呈现。

  DOI：

  10.1039/c4ob00626g

文献信息

• Synthesis of D-Galactopyranosides of trans-4-Hydroxy-L-proline Utilizing the Sulfoxide Glycosylation Method
  作者：C. M. Taylor、C. A. Weir、C. G. Jørgensen

  DOI：10.1071/ch01156

  日期：——

  Phenyl 1-thio-β-D-galactopyranoside (1) was converted into two sulfoxide glycosyl donors: phenyl (2,3,4,6-tetra-O-benzyl)-1-thio-β-D-galactopyranoside S-oxide (3) and phenyl (2,3,4,6-tetra-O-pivaloyl)- 1-thio-β-D-galactopyranoside S-oxide (5). These glycosyl donors were then each reacted with Na- fluorenylmethoxycarbonyl-trans-4-hydroxy-L-proline allyl ester (7). The glycosylation reactions were conducted at -70°C with triflic anhydride as promotor, in the presence of 2,6-di-tert-butyl-4-methylpyridine. In the case of the perbenzylated sulfoxide donor (3), the major product was Na-fluorenylmethoxycarbonyl-trans-4-hydroxy- 4-O-[(2,3,4,6-tetra-O-benzyl)-a-D-galactopyranosyl]-L-proline allyl ester (8a). In dichloromethane, the a-to-β ratio was 3 : 1 and in toluene this improved to 5 : 1, with a combined yield of 41%. In the case of the perpivaloylated sulfoxide donor (5), Na-fluorenylmethoxycarbonyl-trans-4-hydroxy-4-O-[(2,3,4,6-tetra-O-pivaloyl)-β-D- galactopyranosyl]-L-proline allyl ester (9) was obtained as the sole glycoside product in 46% yield.

  将苯基 1-硫代-β-D-吡喃半乳糖苷（1）转化为两种亚砜糖基供体：苯基（2,3,4,6-四-O-苄基）-1-硫代-β-D-吡喃半乳糖苷 S-氧化物（3）和苯基（2,3,4,6-四-O-特戊酰基）-1-硫代-β-D-吡喃半乳糖苷 S-氧化物（5）。然后，这些糖基供体分别与芴甲氧羰基-反式-4-羟基-L-脯氨酸烯丙基酯（7）反应。糖基化反应是在 2,6-二叔丁基-4-甲基吡啶存在下，以三酸酐为促进剂，于 -70°C 温度下进行的。在过苄基亚砜供体（3）的情况下，主要产物为 Na-芴甲氧羰基-反式-4-羟基-4-O-[(2,3,4,6-四-O-苄基)-a-D-吡喃半乳糖基]-L-脯氨酸烯丙基酯（8a）。在二氯甲烷中，a-β 的比例为 3:1，在甲苯中提高到 5:1，总产率为 41%。在过新戊酰化亚砜供体（5）的情况下，Na-芴甲氧羰基-反式-4-羟基-4-O-[(2,3,4,6-四-O-新戊酰基)-β-D-吡喃半乳糖基]-L-脯氨酸烯丙基酯（9）作为唯一的糖苷产物被获得，收率为 46%。
• Total Synthesis and Biological Evaluation of Glycolipids Plakosides A, B and Their Analogs
  作者：Kyriacos C. Nicolaou、Jim Li、Gerhard Zenke

  DOI：10.1002/1522-2675(20000809)83:8<1977::aid-hlca1977>3.0.co;2-d

  日期：2000.8.9

  The total synthesis of plakosides A (1) and B (2), and their designed analogs 3 – 10 was accomplished. The convergent strategy employed involved construction of the individual building blocks employing the Sharpless asymmetric dihydroxylation and the Charette asymmetric cyclopropanation reactions to introduce the desired configuration, followed by their couplings and final elaboration. Thus, key intermediates

  完成了 plakosides A (1) 和 B (2) 及其设计的类似物 3 – 10 的全合成。所采用的收敛策略涉及使用 Sharpless 不对称二羟基化和 Charette 不对称环丙烷化反应构建单个结构单元以引入所需的构型，然后是它们的偶联和最终精细化。因此，关键中间体 12 – 14 以其光学活性形式制备，并通过糖苷化反应和酰胺键形成连接，在适当的加工和最终脱保护后产生目标分子。合成的化合物 1-10 在体外评估了它们的免疫抑制特性，发现只有适度的活性。
• Synthesis, Biological Evaluation, WAC and NMR Studies of<i>S</i>-Galactosides and Non-Carbohydrate Ligands of Cholera Toxin Based on Polyhydroxyalkylfuroate Moieties
  作者：Javier Ramos-Soriano、Ulf Niss、Jesús Angulo、Manuel Angulo、Antonio J. Moreno-Vargas、Ana T. Carmona、Sten Ohlson、Inmaculada Robina

  DOI：10.1002/chem.201302786

  日期：2013.12.23

  The synthesis of several non‐carbohydrate ligands of cholera toxin based on polyhydroxyalkylfuroate moieties is reported. Some of them have been linked to D‐galactose through a stable and well‐tolerated S‐glycosidic bond. They represent a novel type of non‐hydrolyzable bidentate ligand featuring galactose and polyhydroxyalkylfuroic esters as pharmacophoric residues, thus mimicking the GM1 ganglioside

  报道了基于聚羟烷基糠酸酯部分的几种霍乱毒素的非碳水化合物配体的合成。其中一些已通过稳定且耐受良好的S与D-半乳糖相连糖苷键。它们代表了一种新型的不可水解的二齿配体，其特征在于半乳糖和聚羟烷基糠酸酯为药效基团残基，从而模仿了GM1神经节苷脂。通过弱亲和色谱法（WAC）测量了新化合物对霍乱毒素的亲和力。还通过饱和转移差异NMR实验研究了最佳候选物与该毒素的相互作用，该实验可以鉴定与蛋白质相互作用的配体的结合表位。有趣的是，基于聚羟烷基糠酸酯结构的非碳水化合物模拟物显示出最高的亲和力。
• Synthesis of Pyranoid and Furanoid Glycals from Glycosyl Sulfoxides by Treatment with Organolithium Reagents
  作者：Ana M. Gómez、Marta Casillas、Aitor Barrio、Anna Gawel、J. Cristóbal López

  DOI：10.1002/ejoc.200800318

  日期：2008.8

  Glycosyl sulfoxides can be conveniently transformed into pyranoid or furanoid glycals by treatment with organolithium reagents. The more likely reaction pathway involves a sulfoxide/metal exchange reaction to generate a glycosyllithium derivative that undergoes β-elimination of its C-2 substituent. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

  通过用有机锂试剂处理，糖基亚砜可以方便地转化为吡喃或呋喃糖。更可能的反应途径涉及亚砜/金属交换反应以生成糖基锂衍生物，该衍生物经历其 C-2 取代基的 β-消除。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
• [bmim][OTf]: a versatile room temperature glycosylation promoter
  作者：M. Carmen Galan、Claire Brunet、Monica Fuensanta

  DOI：10.1016/j.tetlet.2008.11.042

  日期：2009.1

  [bmim][OTf] is a versatile, ionic liquid promoter for the room temperature glycosylation of both thiophenyl and trichloroacetimidate glycoside donors; the conditions are mild, with no requirement for molecular sieves, and are compatible with a wide range of donors and protecting groups. (c) 2008 Elsevier Ltd. All rights reserved.