2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl iodide | 74638-65-6

• 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-β-D-galactopyranosyl iodide
• 英文别名: [(2R,3S,4S,5R,6S)-3,4,5-triacetyloxy-6-iodooxan-2-yl]methyl acetate
• CAS: 74638-65-6
• 化学式: C₁₄H₁₉IO₉
• 分子量: 458.204
• InChiKey: WOZGYKWDLWNSIZ-MBJXGIAVSA-N

物化性质

• 熔点：
  93-94 °C
• 沸点：
  430.6±45.0 °C(Predicted)
• 密度：
  1.62±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 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：
  114
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl iodide 在 disodium diselenide 、 sodium methylate 作用下， 以 四氢呋喃 、 甲醇 、 水 为溶剂， 反应 10.0h， 生成 bis 1,1’-β-D-galactopyranosyl diselenide
  参考文献：
  名称：

  CN116199728

  摘要：

  公开号：
• 作为产物：
  描述：

  beta-D-半乳糖五乙酸酯 在 碘代三甲硅烷 作用下， 以 氯仿 为溶剂， 反应 0.83h， 生成 2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl iodide
  参考文献：
  名称：

  使用糖基碘和三亚甲基氧对寡糖进行两步官能化及其在多价糖缀合物中的应用

  摘要：

  寡糖结合物，如糖蛋白和糖脂，是潜在的化学治疗剂，也是了解碳水化合物生物学作用的有用工具。随着许多现代分离和合成技术提供了对各种游离糖的访问，对碳水化合物功能化的通用方法的需求日益增加。在此，我们提出一个两步方法论的结合per- Ø -acetylated寡糖功能化的接头，可用于各种显示器。从合成和商业来源获得的寡糖被转化为糖基碘并用 I 2活化形成反应性供体，随后用三亚甲基氧捕获，一步形成碘丙基结合物。末端碘化物作为进一步修饰的化学柄。转化为相应的叠氮化物，然后进行铜催化的叠氮化物-炔烃环加成反应，提供了 Gb3 的多价糖缀合物，用于进一步研究作为抗癌疗法。

  DOI：

  10.1002/chem.201400024

文献信息

• Catalytic Orthogonal Glycosylation Enabled by Enynal‐Derived Copper Carbenes
  作者：Surya Pratap Singh、Bidhan Ghosh、Indrajeet Sharma

  DOI：10.1002/adsc.202301207

  日期：2024.4.23

  earth-abundant copper carbenes. This method operates under mild conditions and employs readily accessible starting materials, including benchtop stable enynal-derived glycosyl donors, synthesized at the gram scale. The reaction accommodates a variety of glycosyl acceptors, including primary, secondary, and tertiary alcohols. The enynal-derived copper carbenes exhibit remarkable reactivity and selectivity

  在此，我们提出了一种利用地球上丰富的铜卡宾进行催化正交糖基化的方法。该方法在温和条件下操作，并采用易于获得的起始材料，包括以克级合成的台式稳定的烯醛衍生糖基供体。该反应适合多种糖基受体，包括伯醇、仲醇和叔醇。烯醛衍生的铜卡宾表现出显着的反应性和选择性，允许与不同的保护基团和立体化学模式形成糖苷键。该方法提供了对 1,2-顺式和 1,2-反式糖苷键的访问。产物的立体选择性与糖基供体的异头构型无关，其也与广泛使用的炔烃和硫代糖苷供体具有正交反应性。三糖的迭代合成进一步证明了这种正交反应性的应用。
• Novel Approaches for the Synthesis and Activation of Thio- and Selenoglycoside Donors
  作者：Silvia Valerio、Alfonso Iadonisi、Matteo Adinolfi、Alessandra Ravidà

  DOI：10.1021/jo070670o

  日期：2007.8.1

  Alkyl thio-, phenyl seleno-, and phenyl thioglycosides can be prepared through short synthetic sequences based on the generation of glycosyl iodides as versatile intermediates. In addition, a novel cheap combined system (stoichiometric NBS and catalytic Bi(OTf)(3)) has been developed for rapid and efficient activation of a wide variety of thio- and selenoglycoside donors.
• Mechanistic studies on the stereoselective formation of glycosyl iodides: first characterization of β-d-glycosyl iodides
  作者：Jacquelyn Gervay、Truc N. Nguyen、Michael J. Hadd

  DOI：10.1016/s0008-6215(96)00321-7

  日期：1997.5

  Treatment of glycosyl acetates with one equivalent of iodotrimethylsilane at low temperature results in the quantitative formation of glycosyl iodides. Carbohydrates that possess a participating group at the C-2 position initially form beta-D-glycosyl iodides, which quickly equilibrate to the alpha-iodo anomers. The beta anomer of peracetylated glucose reacts faster than the alpha anomer, presumably because the C-2 acetate can assist in displacing the silylated anomeric acetate. In contrast, the alpha anomer reacts faster than the beta anomer in substrates lacking a participating group at C-2. For example, activation of 1-O-acetyl-2,3,4,6-tetra-O-benzyl-alpha-D-glucopyranose leads to formation of the beta iodide, while the corresponding beta acetate produces the alpha iodide. Although the beta iodides quickly equilibrate to the alpha anomers, they can be prepared in sizable quantities at low temperatures where equilibration is slow. This report describes the first stereoselective formation and characterization of P-D-glycosyl iodides. (C) 1997 Elsevier Science Ltd.
• [EN] 2'-MODIFIED NUCLEOSIDE BASED OLIGONUCLEOTIDE PRODRUGS<br/>[FR] PROMÉDICAMENTS OLIGONUCLÉOTIDIQUES À BASE DE NUCLÉOSIDES MODIFIÉS EN 2'
  申请人：[en]ALNYLAM PHARMACEUTICALS, INC.

  公开号：WO2022147223A2

  公开（公告）日：2022-07-07

  This invention relates to an oligonucleotide comprising one or more 2'-modified nucleosides, wherein the 2'-position of the nucleoside has a structure of formula (I). The invention also relates to a pharmaceutical composition comprising the oligonucleotide described herein and a method of reducing or inhibiting the expression of a target gene by administering to the subject a therapeutically effective amount of the oligonucleotide described herein. The invention also relates to a method of bioactivating an oligonucleotide comprising one or more 2'-modified nucleosides, wherein the 2'-position of the nucleoside is modified by a bio-cleavable linking group, wherein the bio-cleavable linking group comprises acetal, disulfide, carbamate, amide, sulfonamide, a biocleavable carbohydrate linker, or combinations thereof, said method comprising the step of: exposing the oligonucleotide to a physiological condition that causes the bio-cleavable linking group to be cleaved from the 2'-modified nucleoside, thereby regenerating the 2'-OH group of the nucleoside.