ethyl 2,3,4,6-tetra-O-acetyl-1,5-dithio-α-D-glucopyranoside | 190649-80-0

• 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: ethyl 2,3,4,6-tetra-O-acetyl-1,5-dithio-α-D-glucopyranoside
• 英文别名: [(2R,3S,4S,5R,6S)-3,4,5-triacetyloxy-6-ethylsulfanylthian-2-yl]methyl acetate
• CAS: 190649-80-0
• 化学式: C₁₆H₂₄O₈S₂
• 分子量: 408.494
• InChiKey: PQKIVRIPUWZGTQ-LJIZCISZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  26
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  156
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  ethyl 2,3,4,6-tetra-O-acetyl-1,5-dithio-α-D-glucopyranoside 在 间氯过氧苯甲酸 作用下， 以95%的产率得到Acetic acid (2R,3R,4S,5S,6R)-4,5-diacetoxy-6-acetoxymethyl-2-ethanesulfinyl-tetrahydro-thiopyran-3-yl ester
  参考文献：
  名称：

  Relative Nucleophilicity of the Two Sulfur Atoms in 1,5-Dithioglucopyranoside

  摘要：

  DOI：

  10.1002/anie.199708681
• 作为产物：
  描述：

  五乙酰-5-巯基葡萄糖 、 乙硫醇 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以45%的产率得到ethyl 2,3,4,6-tetra-O-acetyl-1,5-dithio-α-D-glucopyranoside
  参考文献：
  名称：

  糖苷酶抑制剂栗精胺的锍离子类似物的合成和构象分析

  摘要：

  吲哚里西啶生物碱栗精胺的桥头锍盐类似物 (7) 的合成是通过多步程序从 5-硫代-d-吡喃葡萄糖五乙酸酯开始的。该化合物旨在测试以下理论，即吲哚里西啶生物碱的糖苷酶抑制活性可能是由于酶活性位点中带正电物质的静电稳定作用，并且带有永久正电荷的锍盐可能是有利的。双环锍盐 (7) [3(R),4(S),5(R),6(S)-3,4,5-trihydroxy-cis-1-thioniabicyclo[4.3.0]nonane 的结构高氯酸盐]通过 X 射线晶体学证实。化合物7的1H NMR谱分析表明在溶液中采用了相似的构象。这种构象偏好，

  DOI：

  10.1021/ja002038h

文献信息

• A novel 5-thioglycosylation method with 1,5-dithioglycosyl donors: relevance to exo- versus endocyclic activation
  作者：Hideya Yuasa、Osamu Tsuruta、Hironobu Hashimoto

  DOI：10.1016/j.tetlet.2007.09.056

  日期：2007.11

  5-Thioglucosylation of a 1,6-anhydro-2-azido-2-deoxy-beta-D-glucopyranose derivative was carried out with various 1,5-dithioglucosyl donors. The use of per-O-acetyl donors resulted in poor yields of an alpha-disaccharide. On the other hand, per-O-benzyl donors selectively gave an alpha-disaccharide in good to excellent yields regardless of the anomeric configuration of the donors. To study the relevance of the glycosylation results to the pre-equilibrium of exo- versus endocyclic sulfide activation, the relative nucleophilicities of exo- and endocyclic sulfides were estimated from the regioselectivities in the electrophilic oxidation of the per-O-benzyl donors with m-chloroperbenzoic acid. The results obeyed stereoelectronic effects and the endocyclic sulfides were more nucleophilic than the exocyclic sulfides for both anomers of per-O-benzyl-1,5-dithioglucosyl donors, the relative nucleophilicities of the endocyclic over exocyclic sulfides being 67% and 100%, respectively, for the alpha- and beta-anomers. The results of the glycosidation and oxidation suggest that the glycosidation proceeded through an exocyclic cleavage mechanism despite the preferential endocyclic activation of 1,5-dithioglucosides. (c) 2007 Elsevier Ltd. All rights reserved.