p=methylphenyl 2,3,6-tri-O-benzoyl-1-thio-β-D-glucopyranoside | 220645-08-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: p=methylphenyl 2,3,6-tri-O-benzoyl-1-thio-β-D-glucopyranoside
• 英文别名: p-tolyl 2,3,6-tri-O-benzoyl-1-thio-β-D-glucopyranoside；[(2R,3R,4S,5R,6S)-4,5-dibenzoyloxy-3-hydroxy-6-(4-methylphenyl)sulfanyloxan-2-yl]methyl benzoate
• CAS: 220645-08-9
• 化学式: C₃₄H₃₀O₈S
• 分子量: 598.673
• InChiKey: FERRVFPDFKTFGU-PXJJNHDGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  43
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  134
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  p=methylphenyl 2,3,6-tri-O-benzoyl-1-thio-β-D-glucopyranoside 在 二乙胺基三氟化硫 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以75%的产率得到2,3,6-tri-O-benzoyl-4-deoxy-4-S-(4-methoxyphenyl)-4-thio-β-D-galactopyranosyl fluoride
  参考文献：
  名称：

  DAST-Mediated Regioselective Anomeric Group Migration in Saccharides

  摘要：

  When saccharides bearing a sulfur, selenium, or oxygen substituent at the anomeric center and an unprotected hydroxyl group either at C-4 or C-6 were subjected to fluorination with DAST in dichloromethane, a regioselective migration of the anomeric substituent to the C-4 or C-6 position was observed. Certain saccharides gave a mixture of migration and normal fluorination products whereas others yielded mainly or exclusively migration products (beta-glycosyl fluorides). The high thermal and chemical stability of migrated glycosyl fluorides were demonstrated to be an important precursor for many significant carbohydrate analogies. It is therefore suggested that these migrations may have useful applications in organic synthesis.

  DOI：

  10.1021/jo900516r
• 作为产物：
  描述：

  1-硫代-b-甲基葡萄糖甙-4-甲基苯酯 在 吡啶 、 4-二甲氨基吡啶 、 camphor-10-sulfonic acid 、 溶剂黄146 、 三乙胺 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 6.0h， 生成 p=methylphenyl 2,3,6-tri-O-benzoyl-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  Programmable One-Pot Oligosaccharide Synthesis

  摘要：

  In an effort to develop a broadly applicable approach to the facile one-pot synthesis of oligosaccharides, the reactivity of a number of p-methylphenyl thioglycoside (STol) donors which are either fully protected or have one hydroxyl group exposed has been quantitatively determined by HPLC. We have characterized and quantified the influence on reactivity of the structural effects of different monosaccharide cores and different protecting groups on each glycoside donor. In addition, we have established a correlation between glycosyl donor reactivity and the chemical shift of the anomeric proton by H-1 NMR. Using the reactivity data, we have created a database of thioglycosides as glycosyl donors and demonstrated its utility in the easy and rapid one-pot assembly of various linear and branched oligosaccharide structures. In addition, we have developed the first computer program, OptiMer, for use as a database search tool and guide for the selection of building blocks for the one-pot assembly of a desired oligosaccharide or a library of individual oligosaccharides.

  DOI：

  10.1021/ja982232s
• 作为试剂：
  描述：

  N-碘代丁二酰亚胺 、 p-methylphenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-galactopyranoside 在 三氟甲磺酸 、 p=methylphenyl 2,3,6-tri-O-benzoyl-1-thio-β-D-glucopyranoside 作用下， 生成 N-succinimidyl 2,3,4,6-tetra-O-benzyl-β-D-glucopyranoside 、 p-methylphenyl 2,3,6-tri-O-benzoyl-1-thio-4-O-(2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl)-β-D-glucopyranoside
  参考文献：
  名称：

  Programmable One-Pot Oligosaccharide Synthesis

  摘要：

  In an effort to develop a broadly applicable approach to the facile one-pot synthesis of oligosaccharides, the reactivity of a number of p-methylphenyl thioglycoside (STol) donors which are either fully protected or have one hydroxyl group exposed has been quantitatively determined by HPLC. We have characterized and quantified the influence on reactivity of the structural effects of different monosaccharide cores and different protecting groups on each glycoside donor. In addition, we have established a correlation between glycosyl donor reactivity and the chemical shift of the anomeric proton by H-1 NMR. Using the reactivity data, we have created a database of thioglycosides as glycosyl donors and demonstrated its utility in the easy and rapid one-pot assembly of various linear and branched oligosaccharide structures. In addition, we have developed the first computer program, OptiMer, for use as a database search tool and guide for the selection of building blocks for the one-pot assembly of a desired oligosaccharide or a library of individual oligosaccharides.

  DOI：

  10.1021/ja982232s

文献信息

• Iron(<scp>iii</scp>) chloride modulated selective 1,2-trans glycosylation based on glycosyl trichloroacetimidate donors and its application in orthogonal glycosylation
  作者：Mana Mohan Mukherjee、Nabamita Basu、Rina Ghosh

  DOI：10.1039/c6ra21859h

  日期：——

  FeCl3 can also modulate the 1,2-trans selectivity of the reaction of 2-O-alkylated gluco- and galacto-pyranosyl trichloroacetimidates with phenolic compounds leading to the generation of the corresponding β-O-aryl glycosides in excellent yield and selectivity. Apart from these the present methodology has been successfully utilized for double glycosylation and orthogonal glycosylation reactions along

  人们已经集中研究了一种新的糖基化方法，该方法可从10摩尔％的FeCl 3介导的相应的三氯乙酰亚氨酸酯供体有效立体选择性合成β-葡萄糖和半乳糖苷。FeCl 3也已应用于许多基于葡萄糖，半乳糖，甘露糖和鼠李糖的三氯乙酰亚氨酸酯供体，这些供体在C-2位置掺入了各种保护基，从而制备了多种具有优异的1,2-反式选择性的二糖和三糖。FeCl 3还可调节2- O反应的1,2-反式选择性-烷基化的葡糖基和半乳糖基-吡喃糖基三氯乙酰亚胺酸酯与酚类化合物的结合，可导致以优异的产率和选择性生成相应的β- O-芳基糖苷。除此之外，本方法已成功地用于双糖基化和正交糖基化反应，以及在三锅合成的一锅三组分正交糖基化反应中的应用。
• Installation of Electron-Donating Protective Groups, a Strategy for Glycosylating Unreactive Thioglycosyl Acceptors using the Preactivation-Based Glycosylation Method
  作者：Youlin Zeng、Zhen Wang、Dennis Whitfield、Xuefei Huang

  DOI：10.1021/jo801462r

  日期：2008.10.17

  discovered that the introduction of electron-donating protective groups onto the glycosyl donors can considerably enhance their glycosylating power, leading to productive glycosylations even with unreactive acceptors. This observation is quite general and can be extended to a wide range of glycosylation reactions, including one-pot syntheses of chondroitin and heparin trisaccharides. The structures of

  基于预激活的化学选择性糖基化是寡糖合成的一种强大策略，已成功应用于许多复杂寡糖的组装。然而，在带有多个吸电子基团的糖基供体未能糖基化受阻的非反应性受体的反应中遇到了困难。为了克服这个问题，人们发现在糖基供体上引入供电子保护基团可以显着增强其糖基化能力，即使对于不反应的受体也能产生有效的糖基化。这一观察结果非常普遍，可以扩展到广泛的糖基化反应，包括软骨素和肝素三糖的一锅合成。通过低温核磁共振研究确定了预活化时形成的反应中间体的结构。研究发现，对于具有多个吸电子基团的供体，预活化后形成糖基三氟甲磺酸酯，而二恶烯鎓离子是带有供电子保护基团的供体的主要中间体。由于供体在添加受体之前均已完全预激活，因此观察到的这些供体之间的反应性差异并不是由于传统武装-解除武装策略中遇到的选择性激活所致。相反，它是通过受体亲核攻击期间反应中间体和相关的氧碳鎓离子样过渡态之间固有的内能差来合理化的。
• Bromodimethylsulfonium Bromide-Silver Triflate: A New Powerful Promoter System for the Activation of Thioglycosides
  作者：De-Cai Xiong、Li-He Zhang、Xin-Shan Ye

  DOI：10.1002/adsc.200800190

  日期：2008.8.4

  Bromodimethylsulfonium bromide (BDMS) in combination with silver triflate provides a very efficient thiophilic promoter system, capable of activating both “disarmed” and “armed” thioglycosides for glycosidic bond formation. The usefulness of this new promoter is illustrated by a successful reactivity-based one-pot oligosaccharide assembly.

  溴化二甲基溴化溴化铵（BDMS）与三氟甲磺酸银结合提供了一种非常有效的亲硫性助催化剂体系，能够激活“解除武装的”和“武装化的”硫代糖苷以形成糖苷键。成功的基于反应性的一锅寡糖装配说明了这种新启动子的有用性。
• Iterative One-Pot Synthesis of Oligosaccharides
  作者：Xuefei Huang、Lijun Huang、Haisheng Wang、Xin-Shan Ye

  DOI：10.1002/anie.200460176

  日期：2004.10.4
• Efficient activation of thioglycosides with N-(p-methylphenylthio)-ε-caprolactam-TMSOTf
  作者：Sajal Kumar Maity、Nabamita Basu、Rina Ghosh

  DOI：10.1016/j.carres.2012.03.024

  日期：2012.6

  N-(p-Methylphenylthio)-epsilon-caprolactam (1) in combination with trimethylsilyl trifluoromethanesulfonate (TMSOTf) provides an efficient thiophilic promoter system, capable of activating different thioglycosides. Both 'armed' and 'disarmed' thioglycosyl donors were activated for glycosidic bond formation. Notably, this reagent combination works well in reactivity-based one-pot oligosaccharide assembly strategy. (C) 2012 Elsevier Ltd. All rights reserved.