TMS(-2)[TMS(-3)][TMS(-4)]Gal6Ac(b1-4)[TMS(-2)][TMS(-3)]Glc1Ac6Ac | 1547341-20-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: TMS(-2)[TMS(-3)][TMS(-4)]Gal6Ac(b1-4)[TMS(-2)][TMS(-3)]Glc1Ac6Ac
• 英文别名: [(2R,3R,4S,5R)-6-acetyloxy-3-[(2S,3R,4S,5S,6R)-6-(acetyloxymethyl)-3,4,5-tris(trimethylsilyloxy)oxan-2-yl]oxy-4,5-bis(trimethylsilyloxy)oxan-2-yl]methyl acetate
• CAS: 1547341-20-7
• 化学式: C₃₃H₆₈O₁₄Si₅
• 分子量: 829.322
• InChiKey: LOFMASOQMXWVJP-QUGGQHDHSA-N

物化性质

• 沸点：
  647.9±55.0 °C(predicted)
• 密度：
  1.07±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.61
• 重原子数：
  52
• 可旋转键数：
  20
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  153
• 氢给体数：
  0
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  TMS(-2)[TMS(-3)][TMS(-4)]Gal6Ac(b1-4)[TMS(-2)][TMS(-3)]Glc1Ac6Ac 在 4-二甲氨基吡啶 、 碘代三甲硅烷 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 、 氘代苯 为溶剂， 反应 56.0h， 生成 3-iodopropyl (2,3,4,6-tetra-O-acetyl-β-O-D-galactopyranosyl)-(1→4)-O-2,3,6-tri-O-acetyl-β-D-glucopyranoside
  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
• 作为产物：
  描述：

  4-O-[2,3,4,6-tetrakis-O-(trimethylsilyl)-β-D-galactopyranosyl]-1,2,3,6-tetrakis-O-(trimethylsilyl)-D-glucopyranose 、 乙酸酐 在 吡啶 作用下， 以 溶剂黄146 为溶剂， 125.0 ℃ 、275.8 kPa 条件下， 反应 1.25h， 以20%的产率得到(6-O-acetyl-2,3,4-tri-O-trimethylsilyl-β-D-galactopyranosyl)-(1-4)-O-(6-O-acetyl-1,2,3-tri-O-trimethylsilyl)-D-glucopyranoside
  参考文献：
  名称：

  Integrating ReSET with Glycosyl Iodide Glycosylation in Step-Economy Syntheses of Tumor-Associated Carbohydrate Antigens and Immunogenic Glycolipids

  摘要：

  Carbohydrates mediate a wide range of biological processes, and understanding these events and how they might be influenced is a complex undertaking that requires access to pure glycoconjugates. The isolation of sufficient quantities of carbohydrates and glycolipids from biological samples remains a significant challenge that has redirected efforts toward chemical synthesis. However, progress toward complex glycoconjugate total synthesis has been slowed by the need for multiple protection and deprotection steps owing to the large number of similarly reactive hydroxyls in carbohydrates. Two methodologies, regioselective silyl exchange technology (ReSET) and glycosyl iodide glycosylation have now been integrated to streamline the synthesis of the globo series trisaccharides (globotriaose and isoglobotriaose) and alpha-lactosylceramide (alpha-LacCer). These glycoconjugates include tumor-associated carbohydrate antigens (TACAs) and immunostimulatory glycolipids that hold promise as immunotherapeutics. Beyond the utility of the step-economy syntheses afforded by this synthetic platform, the studies also reveal a unique electronic interplay between acetate and silyl ether protecting groups. Incorporation of acetates proximal to silyl ethers attenuates their reactivity while reducing undesirable side reactions. This phenomenon can be used to fine-tune the reactivity of silylated/acetylated sugar building blocks.

  DOI：

  10.1021/jo402736g