4-METHYLPHENYL2,3,4,6-TETRA-O-ACETYL-1-THIO-Β-D-MANNOPYRANOSIDE4-甲基苯基2,3,4,6-四-O-乙酰基-1-硫代-Β-D-吡喃甘露糖苷 | 358681-69-3

• 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
• 中文名称: 4-METHYLPHENYL2,3,4,6-TETRA-O-ACETYL-1-THIO-Β-D-MANNOPYRANOSIDE4-甲基苯基2,3,4,6-四-O-乙酰基-1-硫代-Β-D-吡喃甘露糖苷
• 英文名称: p-methylphenyl 2,3,4,6-tetra-O-acetyl-1-thio-β-D-mannopyranoside
• 英文别名: p-tolyl 2,3,4,6-tetra-O-acetyl-1-thio-α-D-mannopyranoside；p-tolyl 2,3,4,6-tetra-O-acetyl-1-thio-β-D-mannopyranoside；beta-D-Mannopyranoside, 4-methylphenyl 1-thio-, 2,3,4,6-tetraacetate；[(2R,3R,4S,5S,6S)-3,4,5-triacetyloxy-6-(4-methylphenyl)sulfanyloxan-2-yl]methyl acetate
• CAS: 358681-69-3
• 化学式: C₂₁H₂₆O₉S
• 分子量: 454.498
• InChiKey: XRFOIRMXQHXTRL-MJCUULBUSA-N

物化性质

• 沸点：
  524.5±50.0 °C(Predicted)
• 密度：
  1.29±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  31
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.52
• 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：

  4-METHYLPHENYL2,3,4,6-TETRA-O-ACETYL-1-THIO-Β-D-MANNOPYRANOSIDE4-甲基苯基2,3,4,6-四-O-乙酰基-1-硫代-Β-D-吡喃甘露糖苷 在 吡啶 、 甲醇 、 三氟甲磺酸三甲基硅酯 、 sodium methylate 、 sodium hydride 、 对甲苯磺酸 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 生成 p-tolyl 4,6-di-O-acetyl-2,3-di-O-benzyl-1-thio-α-D-mannopyranoside
  参考文献：
  名称：

  Mannopyranosyl Uronic Acid Donor Reactivity

  摘要：

  The reactivity of a variety of mannopyranosyl uronic acid donors was assessed In a set of competition experiments, in which two (S)-tolyl mannosyl donors were made to compete for a limited amount of promoter (NIS/TfOH). These experiments revealed that the reactivity of mannuronic acid donors is significantly higher than expected based on the electron-withdrawing capacity of the C-5 carboxylic acid ester function. A 4-O-acetyl-beta-(S)-tolyl mannuronic acid donor was found to have similar reactivity as per-O-benzyl-alpha-(S)-tolyl mannose.

  DOI：

  10.1021/ol2016862
• 作为产物：
  描述：

  Α-D-五乙酸甘露糖酯 在 氢溴酸 、 sodium hydride 、 溶剂黄146 作用下， 以 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 3.0h， 生成 4-METHYLPHENYL2,3,4,6-TETRA-O-ACETYL-1-THIO-Β-D-MANNOPYRANOSIDE4-甲基苯基2,3,4,6-四-O-乙酰基-1-硫代-Β-D-吡喃甘露糖苷
  参考文献：
  名称：

  Mannopyranosyl Uronic Acid Donor Reactivity

  摘要：

  The reactivity of a variety of mannopyranosyl uronic acid donors was assessed In a set of competition experiments, in which two (S)-tolyl mannosyl donors were made to compete for a limited amount of promoter (NIS/TfOH). These experiments revealed that the reactivity of mannuronic acid donors is significantly higher than expected based on the electron-withdrawing capacity of the C-5 carboxylic acid ester function. A 4-O-acetyl-beta-(S)-tolyl mannuronic acid donor was found to have similar reactivity as per-O-benzyl-alpha-(S)-tolyl mannose.

  DOI：

  10.1021/ol2016862

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。
• Novel Efficient Routes to Heparin Monosaccharides and Disaccharides Achieved via Regio- and Stereoselective Glycosidation
  作者：Henry N. Yu、Jun-ichi Furukawa、Tsuyoshi Ikeda、Chi-Huey Wong

  DOI：10.1021/ol036390m

  日期：2004.3.1

  methodology for the synthesis of heparin building blocks has been developed. We describe novel efficient routes to both L-iduronic acid and D-glucuronic acid acceptors. Glycosylation with thioglycosides donors gave corresponding disaccharides in a regio- and stereoselective fashion. An improved approach to synthesizing azido-glucose thioglycoside donor to render azido-sugar from mannose via nucleophilic substitution

  已经开发了合成肝素构件的新方法。我们描述了新颖的有效途径，既L-艾杜糖酸和D-葡萄糖醛酸受体。用硫糖苷供体的糖基化以区域和立体选择性的方式给出了相应的二糖。描述了一种合成叠氮基葡萄糖硫代糖苷供体以通过亲核取代从甘露糖产生叠氮基糖的改进方法。[反应：看文字]
• A versatile glycosylation strategy via Au(<scp>iii</scp>) catalyzed activation of thioglycoside donors
  作者：Amol M. Vibhute、Arun Dhaka、Vignesh Athiyarath、Kana M. Sureshan

  DOI：10.1039/c6sc00633g

  日期：——

  Among various methods of chemical glycosylations, glycosylation by activation of thioglycoside donors using a thiophilic promoter is an important strategy. Many promoters have been developed for the activation of thioglycosides. However, incompatibility with substrates having alkenes and the requirement of a stoichiometric amount of promoters, co-promoters and extreme temperatures are some of the limitations

  在各种化学糖基化方法中，通过使用亲硫性启动子活化硫代糖苷供体的糖基化是重要的策略。已经开发了许多用于硫糖苷活化的启动子。然而，与具有烯烃的底物的不相容性以及对化学计量量的促进剂，助促进剂和极端温度的要求是一些限制。我们已经开发了一种通过使用催化量的AuCl 3激活硫代糖苷供体来进行糖基化的有效方法并且没有任何共同发起人。该反应非常快，高产率并且在室温下非常容易。该方法的多功能性从环境条件下与武装和解除武装的供体和空间要求的底物（受体/供体）的容易糖基化，常见保护基团的稳定性以及含烯烃底物的相容性中可以明显看出。反应。
• Boron-Promoted Umpolung Reaction of Sulfonyl Chlorides for the Stereospecific Synthesis of Thioglycosides via Reductive Deoxygenation Coupling Reactions
  作者：Siyu Li、Yujuan Wang、Lei Zhong、Siyu Wang、Zhengli Liu、Yuanwei Dai、Yun He、Zhang Feng

  DOI：10.1021/acs.orglett.2c00353

  日期：2022.4.8

  potential. Herein we disclose an efficient method for the stereospecific synthesis of 1-thioglycosides via a boron-promoted reductive deoxygenation coupling reaction from readily accessible sulfonyl chlorides and glycosyl bromides. Our protocol features mild conditions and excellent functional group tolerance and stereoselectivity. The translational potential of this metal-free approach is demonstrated

  S-糖苷具有广泛的生物活性并作为天然O-糖苷对应物的稳定模拟物，因此具有巨大的治疗潜力。在这里，我们公开了一种通过硼促进的还原脱氧偶联反应从容易获得的磺酰氯和糖基溴化物立体定向合成 1-硫糖苷的有效方法。我们的协议具有温和的条件和出色的官能团耐受性和立体选择性。这种无金属方法的转化潜力通过天然产物和药物分子的后期糖多样化得到证明。
• Solvent free, catalytic and diastereoselective preparation of aryl and alkyl thioglycosides as key components for oligosaccharide synthesis
  作者：Daniel L. Jensen、Helle H. Trinderup、Frederik Skovbo、Henrik H. Jensen

  DOI：10.1039/d2ob00939k

  日期：——

  A new and environmentally friendly protocol for the conversion of sugar per-acetates into thioglycosides under solvent free and catalytic conditions is presented. The procedure involves heating in the presence of InCl3 and various aryl thiols. For alkyl thioglycoside synthesis, cyclohexane thiol was found to give good results and yield a glycosyl donor with reactivity similar to a thioethyl congener

  提出了一种在无溶剂和催化条件下将糖过乙酸转化为硫糖苷的新的环保方案。该过程包括在 InCl 3和各种芳基硫醇存在下加热。对于烷基硫代糖苷的合成，发现环己烷硫醇产生了良好的结果并产生了具有与硫乙基同系物相似的反应性的糖基供体。发现建立的最佳反应条件即使在以多克规模进行时也能以简单且高度非对映选择性的方式提供所需的硫糖苷产物。