o-tolyl 4,6-di-O-acetyl-2,3-dideoxy-1-thio-α-D-erythro-hex-2-enopyranoside | 557104-54-8

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: o-tolyl 4,6-di-O-acetyl-2,3-dideoxy-1-thio-α-D-erythro-hex-2-enopyranoside
• 英文别名: ((2R,3R,4S)-3-acetoxy-4-(o-tolylthio)-3,4-dihydro-2H-pyran-2-yl)methyl acetate；[(2R,3S,6R)-3-acetyloxy-6-(2-methylphenyl)sulfanyl-3,6-dihydro-2H-pyran-2-yl]methyl acetate
• CAS: 557104-54-8
• 化学式: C₁₇H₂₀O₅S
• 分子量: 336.409
• InChiKey: AFZZSGCVEXOBDN-ZMSDIMECSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  87.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  2-巯基甲苯 、 乙酰化葡萄烯糖 在 碘 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 以85%的产率得到o-tolyl 4,6-di-O-acetyl-2,3-dideoxy-1-thio-α-D-erythro-hex-2-enopyranoside
  参考文献：
  名称：

  Highly Stereoselective Synthesis of 2,3-Unsaturated Thioglycopyranosides Employing Molecular Iodine

  摘要：

  首次利用分子碘实现了d-甘露二糖型糖类的硫代糖基化反应，与各种硫醇反应以高产率得到相应的2,3-不饱和硫代糖苷。在三-O-乙酰基-d-甘露二糖型糖类的情况下，仅获得了α-异构体。由于使用了易获得的碘，这种方法非常简单、便捷且实用。

  DOI：

  10.1055/s-0029-1218722

文献信息

• Acid Catalyzed Stereocontrolled Ferrier-Type Glycosylation Assisted by Perfluorinated Solvent
  作者：Zhiqiang Lu、Yanzhi Li、Shaohua Xiang、Mengke Zuo、Yangxing Sun、Xingxing Jiang、Rongkai Jiao、Yinghong Wang、Yuqin Fu

  DOI：10.3390/molecules27217234

  日期：——

  stereoselective formation of O-/S-glycosidic linkages that occurs via a Ferrier rearrangement of acetylated glycals. In this system, the weak interactions between perfluoro-n-hexane and substrates could augment the reactivity and stereocontrol. The initiation of transformation requires only an extremely low loading of resin-H+ and the mild conditions enable the accommodation of a broad spectrum of glycal donors

  本文描述的是全氟化溶剂在通过乙酰化糖醛的费里尔重排发生的O-/S-糖苷键的立体选择性形成中的首次应用。在该系统中，全氟正己烷和底物之间的弱相互作用可以增强反应性和立体控制。转化的启动仅需要极低的树脂-H +负载，并且温和的条件能够容纳广谱的糖供体和受体。这种化学物质的“绿色”特征体现在培养基的低毒性和易于回收以及产品分离操作的简单性。
• Ferrier rearrangement promoted by an electrochemically generated zirconium catalyst
  作者：Dragana Stevanović、Anka Pejović、Ivan Damljanović、Aleksandra Minić、Goran A. Bogdanović、Mirjana Vukićević、Niko S. Radulović、Rastko D. Vukićević

  DOI：10.1016/j.carres.2015.02.001

  日期：2015.4

  In situ generated zirconium catalyst from a sacrificial zirconium anode was successfully applied to promote Ferrier rearrangement of 3,4,5-tri-O-acetyl-D-glucal and 6-deoxy-3,4-di-O-acetyl-L-glucal (3,4-di- O-acetyl-L-rhamnal) in the presence of three thiols and eleven thiophenols as nucleophiles. A simple constant current electrolysis (20 mA, 0.4 F mol(-1)) of an acetonitrile solution of lithium perchlorate (0.1 M) containing the corresponding glycal and S-nucleophiles, using a zirconium anode and a platinum cathode resulted in the successful synthesis of the corresponding 2,3-unsaturated peracetylated thioglycosides (with an average anomer ratio alpha/beta-4.129 in the case of peracetylated D-glucal and 8.740 in the case of L-rhamnal). The same procedure proved to be appropriate in synthesizing dihydropyran derivatives ('C-glycosides') using allyltrimethylsilane as the nucleophile (only 'alpha-anomers' were obtained). All new compounds were fully characterized by spectral data, whereas single-crystal X-ray analysis was performed for two thioglycosides. (C) 2015 Elsevier Ltd. All rights reserved.