2,3,4,6-tetra-O-acetyl-1-thio-D-glucopyranose | 72541-16-3

• 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
• 英文名称: 2,3,4,6-tetra-O-acetyl-1-thio-D-glucopyranose
• 英文别名: [(2R,3R,4S,5R)-3,4,5-triacetyloxy-6-sulfanyloxan-2-yl]methyl acetate
• CAS: 72541-16-3
• 化学式: C₁₄H₂₀O₉S
• 分子量: 364.373
• InChiKey: SFOZKJGZNOBSHF-RQICVUQASA-N

物化性质

• 沸点：
  425.5±45.0 °C(Predicted)
• 密度：
  1.31±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  24
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  115
• 氢给体数：
  1
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  2,3,4,6-tetra-O-acetyl-1-thio-D-glucopyranose 在 sodium methylate 、 三氟乙酸 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 1.5h， 生成 (2R,3S,4S,5R,6S)-2-(hydroxymethyl)-6-(9H-xanthen-9-ylsulfanyl)oxane-3,4,5-triol
  参考文献：
  名称：

  The S -xanthenyl group: potential for application in the synthesis of thioglycosides

  摘要：

  The S-xanthenyl (Xan) group was demonstrated to have potential as a convenient protecting group for 1-thiosugars in the synthesis of thioglycosides. Easily introduced by reaction of a 1-thiosugar with 9-hydroxyxanthene in the presence of catalytic TFA, the S-Xan group is compatible with a wide range of functionalities and protecting groups. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)02070-1
• 作为产物：
  描述：

  2,3,4,6-四乙酰氧基-alpha-D-吡喃葡萄糖溴化物 在 硫脲 作用下， 以 丙酮 、 二氯甲烷 、 水 为溶剂， 反应 29.0h， 以76%的产率得到2,3,4,6-tetra-O-acetyl-1-thio-D-glucopyranose
  参考文献：
  名称：

  Synthesis of Abietane-derived Disulfides with Monosaccharide Fragments

  摘要：

  A series of asymmetric disulfides was obtained in yields of 38-50% by the co-oxidation of a mixture of diterpene abietane-derived thiols and thiols synthesized from protected monosaccharides with galacto-, fructo-, and glucopyranose and ribofuranose fragments. After removal of the acetyl protection in the disulfide containing 1,2,3,4-tetra-O-acetyl-beta-D-glucopyranose and dehydroabietane moieties, a disulfide with free glucose hydroxyl groups was obtained in a yield of 94%.

  DOI：

  10.1134/s1070428020080096

文献信息

• Reactivity of Auranofin with Selenols and Thiols – Implications for the Anticancer Activity of Gold(I) Compounds
  作者：Francesca Di Sarra、Barbara Fresch、Riccardo Bini、Giacomo Saielli、Alessandro Bagno

  DOI：10.1002/ejic.201300058

  日期：2013.5.14

  electrophilic molecules, including the AuI complex auranofin [2,3,4,6-tetra-O-acetyl-1-thio-β-D-glucopyranosato-S-(triethylphosphane)gold]. The reactions between auranofin and models of thiol and selenol nucleophiles present in TrxR (PhSH and PhSeH) have been investigated in chloroform and methanol by means of 1H, 31P, and 77Se NMR spectroscopy. In chloroform, auranofin undergoes ligand substitution of the te

  硫氧还蛋白还原酶 (TrxR) 作为癌症治疗的潜在靶点引起了人们的极大兴趣。催化位点中硒原子的存在使其对亲电分子的抑制敏感，包括 AuI 复合物金诺芬 [2,3,4,6-四-O-乙酰-1-硫代-β-D-吡喃葡萄糖-S -(三乙基膦)金]。已通过 1H、31P 和 77Se NMR 光谱在氯仿和甲醇中研究了金诺芬与 TrxR（PhSH 和 PhSeH）中存在的硫醇和硒醇亲核试剂模型之间的反应。在氯仿中，金诺芬的四乙酰硫代葡萄糖部分被 PhS 或 PhSe 基团取代。该反应在两种情况下都是可逆的，但其特点是平衡常数大不相同（S 约为 1，Se 至少为 103）。在极性溶剂中，如甲醇，反应更复杂，磷烷部分也进行配体交换。通过对 Et3PAuCl 的研究，已经阐明了一些特征。所涉及的基本过程已通过 DFT 计算进行了表征。
• Steric and stereoscopic disulfide construction for cross-linkage <i>via N</i>-dithiophthalimides
  作者：Wen-Chao Gao、Jun Tian、Yu-Zhu Shang、Xuefeng Jiang

  DOI：10.1039/d0sc01060j

  日期：——

  Disulfide bonds are a significant motif in life and drug-delivery systems. In particular, steric hindrance and stereoscopic disulfide linkers are closely associated with the stability of antibody–drug conjugates, which affects the potency, selectivity, and pharmacokinetics of drugs. However, limited availability and diversity of tertiary thiols impede the construction of steric and stereoscopic disulfides

  二硫键是生命和药物输送系统中的重要主题。特别是，位阻和立体二硫键与抗体-药物偶联物的稳定性密切相关，这会影响药物的效力，选择性和药代动力学。但是，叔硫醇的可用性和多样性有限，阻碍了在生物化学和药物中用于交联的空间和立体二硫化物的构建。通过调节脱硫试剂的掩膜效应，我们开发了一种简便而稳健的策略，可通过N构建多种空间和立体二硫化物。-二硫代邻苯二甲酰亚胺。通过受阻的二硫键成功地建立了包括氨基酸，糖类和核苷在内的生物分子与不同药物和荧光分子的实际交联。
• A new glycosidation method through nitrite displacement on substituted nitrobenzenes
  作者：Xavier Álvarez-Micó、Mario J.F. Calvete、Michael Hanack、Thomas Ziegler

  DOI：10.1016/j.carres.2006.11.017

  日期：2007.2

  protected 1-OH and 1-SH glycoses in the glucose, glucosamine, galactose, mannose, and lactose series react with nitrobenzenes activated by one or two electron withdrawing substituents like nitro and cyano to afford the corresponding aryl glycosides in 50-100% yield. The S(N)Ar displacement of nitrite by 1-OH glycoses is reversible and gives predominantly the alpha-glycosides, whereas 1-SH glycoses do not

  葡萄糖，葡糖胺，半乳糖，甘露糖和乳糖系列中的苄基，苯甲酰基和乙酰基保护的1-OH和1-SH糖基与由一个或两个吸电子取代基（如硝基和氰基）活化的硝基苯反应，得到相应的芳基糖苷50-100％的产率。1-OH糖苷对亚硝酸盐的S（N）Ar置换是可逆的，并且主要产生α-糖苷，而1-SH糖苷则不会发生异化作用而提供β-糖苷。因此，制备的二氰基苯基糖苷是用于通过模板合成制备酞菁-糖缀合物的有用的结构单元。
• Remote Activation of Disarmed Thioglycosides in Latent-Active Glycosylation via Interrupted Pummerer Reaction
  作者：Xiong Xiao、Yueqi Zhao、Penghua Shu、Xiang Zhao、Yan Liu、Jiuchang Sun、Qian Zhang、Jing Zeng、Qian Wan

  DOI：10.1021/jacs.6b08305

  日期：2016.10.12

  yields. Meanwhile, observation of thiosulfinate, thiosulfonate, and disulfide suggested that the leaving group was activated via an interrupted Pummerer reaction. The disarmed SPSB thioglycosyl donors could be selectively activated in the presence of various thioglycosides with remote activation mode. Finally, two natural hepatoprotective glycosides, Leonoside E and Leonuriside B, were efficiently synthesized

  S-糖苷，即 S-2-(2-丙硫基) 苄基 (SPTB) 糖苷，通过简单的选择性氧化被转化为相应的氧化糖基供体 S-2-(2-丙基亚磺酰基) 苄基 (SPSB) 糖苷。用三氟甲磺酸酐处理解除武装的 SPSB 供体和各种受体，以良好到极好的产率提供所需的糖苷。同时，对硫代亚磺酸盐、硫代磺酸盐和二硫化物的观察表明离去基团是通过中断的普默勒反应激活的。解除武装的 SPSB 硫糖基供体可以在各种硫糖苷的存在下以远程激活模式被选择性地激活。最后，使用这种新开发的方法以收敛的方式有效地合成了两种天然的保肝糖苷，Leonoside E 和 Leonuriside B。
• Thio-sugars. Part 5: From d-glucal to 3-deoxy-(1→2)-2-S-thiodisaccharides through isolevoglucosenone—a simple approach
  作者：Zbigniew J Witczak、Hong Chen、Peter Kaplon

  DOI：10.1016/s0957-4166(99)00567-4

  日期：2000.2

  conjugate addition of 1-thiosugars to isolevoglucosenone followed by the reduction of the C-4 keto function constitute a new two-step general approach to these classes of biologically important thio-sugars.

  描述了一种新的异硫葡糖苷酮的合成及其立体选择性官能化成3-脱氧-（1-2）-2- S-硫代二糖的方法。将1-硫代糖碱催化的共轭加成至异硫葡糖醛酮，然后降低C-4酮功能，构成了对这些类别的重要生物学硫代糖的新的两步通用方法。