α-D-glucopyranosyl-(1->4)-α-D-glucopyranosyl-(1->4)-β-D-glucopyranosyl azide

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: α-D-glucopyranosyl-(1->4)-α-D-glucopyranosyl-(1->4)-β-D-glucopyranosyl azide
• 英文别名: β-D-maltotriosyl azide；Glc(a1-4)Glc(a1-4)Glc(b)-N3；(2R,3R,4S,5S,6R)-2-[(2R,3S,4R,5R,6R)-6-[(2R,3S,4R,5R,6R)-6-azido-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol
• 化学式: C₁₈H₃₁N₃O₁₅
• 分子量: 529.455
• InChiKey: GNYVLQNMJQYRKX-WUZXSGHDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -5.3
• 重原子数：
  36
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  263
• 氢给体数：
  10
• 氢受体数：
  17

反应信息

• 作为反应物：
  描述：

  α-D-glucopyranosyl-(1->4)-α-D-glucopyranosyl-(1->4)-β-D-glucopyranosyl azide 在 palladium on activated charcoal 氢气 、 三氟乙酸 作用下， 以 N-甲基吡咯烷酮 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 6.0h， 生成 (2S)-4-[[(2R,3R,4R,5S,6R)-5-[(2R,3R,4R,5S,6R)-3,4-dihydroxy-6-(hydroxymethyl)-5-[(2R,3R,4S,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]oxy-3,4-dihydroxy-6-(hydroxymethyl)oxan-2-yl]amino]-2-(9H-fluoren-9-ylmethoxycarbonylamino)-4-oxobutanoic acid
  参考文献：
  名称：

  Efficient Synthesis of Complex Glycopeptides Based on Unprotected Oligosaccharides

  摘要：

  N-Glycopeptides containing 1 to 4 trisaccharide chains, with the carbohydrates vicinal to each other in the multivalent glycopeptides, were efficiently synthesized by using the glycosylated Fmoc-asparagine as a key building block. While the couplings of amino acids with glycopeptides could be achieved in the homogeneous solutions in N-methylpyrrolidinone (NMP) to give excellent yields, all products were conveniently isolated from the reaction mixtures through a precipitation method by using the free carbohydrate chains as phase tags. Commercially available pentafluorophenyl (Pfp) esters of amino acids were employed for the glycopeptide elongation. Longer glycopeptides were constructed by means of a highly convergent synthetic design that is based on the coupling of glycopeptide/peptide fragments. Hydrogen bond interactions between free oligosaccharides were proposed to explain the exceptionally high efficiency of the couplings between two glycosylated building blocks.

  DOI：

  10.1021/jo020570c
• 作为产物：
  描述：

  maltotriose 在 sodium azide 、 2-氯-1,3-二甲基氯化咪唑啉 、 N,N-二异丙基乙胺 作用下， 以 重水 为溶剂， 反应 0.5h， 以78%的产率得到α-D-glucopyranosyl-(1->4)-α-D-glucopyranosyl-(1->4)-β-D-glucopyranosyl azide
  参考文献：
  名称：

  One-step conversion of unprotected sugars to β-glycosyl azides using 2-chloroimidazolinium salt in aqueous solution

  摘要：

  在 2-氯-1,3-二甲基氯化咪唑啉（DMC）的介导下，通过非保护糖和叠氮化钠的反应，在水中直接合成了各种δ-糖基叠氮化物。

  DOI：

  10.1039/b905761g

文献信息

• Regioselective oxidation of unprotected 1,4 linked glucans
  作者：Niek N. H. M. Eisink、Jonas Lohse、Martin D. Witte、Adriaan J. Minnaard

  DOI：10.1039/c6ob00608f

  日期：——

  Palladium-catalyzed alcohol oxidation allows the chemo- and regioselective modification of unprotected 1,4 linked glucans. This is demonstrated in the two-step bisfunctionalization of 1,4 linked glucans up to the 7-mer. Introduction of an anomeric azide is followed by a highly regioselective mono-oxidation of the terminal C3–OH functionality. The resulting orthogonal bis-functionalized oligosaccharides

  钯催化的醇氧化可以对未保护的1,4连接的葡聚糖进行化学和区域选择性修饰。1,7连接的葡聚糖直至7-mer的两步双功能化证明了这一点。引入端基叠氮化物后，对末端C3-OH官能团进行高度区域选择性的单氧化。如4-草酸巴豆酸酯互变异构酶的半胱氨酸突变体与生物素的缀合所证明的，所得的正交双官能化寡糖是PEG-间隔子的可行替代物。
• A Facile Synthesis of<i>N</i>^γ-Glycosyl Asparagine Conjugates and Short<i>N</i>-Linked Glycopeptides
  作者：Jie Xue、Min Guo、Guofeng Gu、Zhongwu Guo

  DOI：10.1080/07328303.2011.633723

  日期：2012.2

  Both free and protected glycosyl azides were efficiently coupled to the side chain of aspartate by the Staudinger reaction for the synthesis of N γ-glycosyl asparagine conjugates and short N-linked glycopeptides that can be employed to construct complex N-linked glycopeptides. In the process, a facile two-step protocol was developed for free glycosyl azide synthesis, which includes reported direct transformation

  游离和保护的糖基叠氮化物通过用于合成的施陶丁格反应中有效地耦合到天冬氨酸的侧链Ñ γ α-糖基天冬酰胺的共轭和短ñ -连接的可被采用来构建复杂的糖肽ñ -连接的糖肽。在此过程中，开发了一种用于游离糖基叠氮化物合成的简便的两步方案，该方法包括据报道通过与碳酸氢铵反应将游离寡糖直接转化为糖基胺，然后进行立体定向重氮转移反应将糖基胺转化为糖基叠氮化物。