methyl 3-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosylthio)propanoate | 3254-09-9

• 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: methyl 3-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosylthio)propanoate
• 英文别名: methyl 3-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosylthio)propionate；3--propionsaeure-methylester；3-(Tetra-O-acetyl-β-D-glucopyranosylmercapto)-propionsaeure-methylester；methyl 3-[(2S,3R,4S,5R,6R)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]sulfanylpropanoate
• CAS: 3254-09-9
• 化学式: C₁₈H₂₆O₁₁S
• 分子量: 450.464
• InChiKey: JFHHMLAFTNRIQT-LHKMKVQPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  30
• 可旋转键数：
  14
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  166
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  methyl 3-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosylthio)propanoate 在 sodium tungstate 、 双氧水 作用下， 以 甲醇 为溶剂， 以39%的产率得到methyl 3-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosylthio)propanoate S-oxide
  参考文献：
  名称：

  Synthesis of anomeric sulfonamides and their behaviour under radical-mediated bromination conditions

  摘要：

  O-Peracetylated methyl 3-(D-glycopyranosylthio)propanoates of beta-D-gluco, and alpha- and beta-D-galacto configurations were oxidized to the corresponding S,S-dioxides (sulfones) by Oxone (R) or MCPBA. Oxidation of the beta-D-gluco derivative with H2O2/Na2WO4 gave the corresponding S-oxide (sulfoxide). DBU-induced elimination of methyl acrylate from the P-D-gluco and P-D-galacto configured SS-dioxides (sulfones) gave O-peracetylated beta-D-glycopyranosyl-1-C-sulfinates which, on treatment with H2NOSO3H, furnished the corresponding beta-D-glycopyranosyl-1-C-sulfonamides. Radical-mediated bromination of the protected methyl 3-(beta-D-glycopyranosylthio)propanoate S.S-dioxides gave mixtures of 1-C- and 5-C-bromoglycosyl compounds. Similar brominations of the O-peracetylated beta-D-glycopyranosyl-1-C-sulfonamides resulted in the formation Of U-D-glycopyranosyl bromides and 1-C- and 5-C-bromoglycosyl sulfonamides. A rationale for these observations was proposed. Methyl 3-(beta-D-glucopyranosylthio)propanoate, its S,S-dioxide, and beta-D-glucopyranosyl-1-C-sulfonamide proved inefficient when tested as inhibitors of rabbit muscle glycogen phosphorylase b. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2008.11.002
• 作为产物：
  描述：

  丙烯酸甲酯（MA） 、 2,3,4,6-四乙酰氧基-alpha-D-吡喃葡萄糖溴化物 在 benzyltriethylammonium tetrathiomolybdate 作用下， 以 乙腈 为溶剂， 反应 5.0h， 以95%的产率得到methyl 3-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosylthio)propanoate
  参考文献：
  名称：

  通过四硫代钼酸盐介导的掩蔽硫醇盐的迈克尔加成合成硫糖苷

  摘要：

  通过使用四硫代钼酸苄基三乙基铵 $[{(BnNEt_3)}_2MoS_4; 在中性条件下以优异的收率合成硫糖苷的有效一锅法；1]$ 作为硫转移试剂已被开发出来。试剂 1 与糖卤化物反应生成糖二硫化物，然后进行原位还原裂解以提供相应的硫醇盐，然后通过迈克尔加成得到相应的硫代糖苷。此外，通过使用四硫代钼酸铵 $[{(NH_4)}_2 MoS_4; 2]$。这种方法的应用已扩展到通过分子间和分子内反应合成具有优异非对映选择性的各种硫糖类似物。

  DOI：

  10.1002/ejoc.200400360

文献信息

• Generation and Use of Glycosyl Radicals under Acidic Conditions: Glycosyl Sulfinates as Precursors
  作者：Shiyang Xu、Wei Zhang、Caiyi Li、Yanjing Li、Hongxin Zeng、Yingwei Wang、Yang Zhang、Dawen Niu

  DOI：10.1002/anie.202218303

  日期：——

  Glycosyl radicals were generated under acidic conditions for the first time by the use of glycosyl sulfinates as precursors. This development enables the installation of glycosyl units directly onto pharmaceutically relevant pyridine cores by the Minisci reaction.

  通过使用糖基亚磺酸盐作为前体，首次在酸性条件下产生糖基自由基。这一发展使得糖基单元能够通过 Minisci 反应直接安装到药学相关的吡啶核心上。