N^α-carbobenzyloxy-N^γ-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-L-asparagine-O-methyl ester

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: N^α-carbobenzyloxy-N^γ-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-L-asparagine-O-methyl ester
• 英文别名: Nα-(benzyloxycarbonyl)-Nγ-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-L-asparagine O-methyl ester；methyl (2S)-4-oxo-2-(phenylmethoxycarbonylamino)-4-[[(2R,3R,4S,5R,6R)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]amino]butanoate
• 化学式: C₂₇H₃₄N₂O₁₄
• 分子量: 610.572
• InChiKey: ZQAPFCAQBOAMSM-VQLLNBNUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  43
• 可旋转键数：
  18
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  208
• 氢给体数：
  2
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  N^α-carbobenzyloxy-N^γ-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-L-asparagine-O-methyl ester 、 甘氨酰胺 在 Alcalase 作用下， 以 2-甲基-2-丁醇 、 N,N-二甲基甲酰胺 为溶剂， 以38%的产率得到Cbz-L-(N-1-Glu(Ac)4-Asn)-Gly-NH2
  参考文献：
  名称：

  Cu-Catalyzed Formation of Triazole-Linked Glycoamino Acids and Application in Chemoenzymatic Peptide Synthesis

  摘要：

  Novel stable triazole-linked glycoamino acids have been prepared, with the heterocyclic moiety being established by efficient Cu-mediated cycloaddition between the corresponding azido and acetylene moieties. Selected reactions were scaled up and successfully subjected to chemoenzymatic peptide-coupling reactions involving the proteolytic enzyme alcalase, resulting in several glycosylated di- and tripeptide structures. Since chemoenzymatic approaches have several advantages over chemical peptide coupling, especially concerning large-scale peptide synthesis, these results may be regarded as initial steps in the direction of production via fully chemoenzymatic peptide synthesis.

  DOI：

  10.1021/op700249f
• 作为产物：
  描述：

  β-D-葡萄糖五乙酸酯 在 三氯化铝 叠氮基三甲基硅烷 、 四丁基氟化铵 、 水 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基乙酰胺 为溶剂， 反应 56.0h， 生成 N^α-carbobenzyloxy-N^γ-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-L-asparagine-O-methyl ester
  参考文献：
  名称：

  糖基叠氮化物与三芳基膦的无痕Staudinger连接：糖基酰胺的立体选择性合成†

  摘要：

  α-糖基酰胺可通过无痕施陶丁格与二苯基膦酰基-苯基酯的连接由相应的O-苄基-α-糖基叠氮化物合成4。所用的所有膦及其苯酚前体在4°C的空气中均可保持稳定数月。还原中间体的快速分子内捕集导致酰胺键的直接形成，继而防止了差向异构化并允许在异头碳上保留构型。当反应在极性非质子溶剂中进行时，产率和α-选择性高。苄基醚保护基的去除是通过催化氢化来实现的。α-糖基酰胺代表了一类实际上未开发的不可水解的单糖衍生物，可以作为糖模拟物找到有用的应用。NMR光谱的构象研究证实，葡萄糖，半乳糖和fuco系列中的脱保护α-糖基酰胺保留了单糖的正常吡喃糖构象。膦的反应4用四ø -乙酰基葡糖基叠氮化物是nonstereoconservative，并在良好的产率，并与来自两个α和β叠氮化物开始完整的立体选择性获得β糖基酰胺。

  DOI：

  10.1021/jo060409s

文献信息

• Stereoselective Synthesis of<i>N</i>-Glycosyl Amino Acids by Traceless Staudinger Ligation of Unprotected Glycosyl Azides
  作者：Filippo Nisic、Manuel Andreini、Anna Bernardi

  DOI：10.1002/ejoc.200900692

  日期：2009.11

  stereoconservative Staudinger ligation of unprotectedα- and β-glycosyl azides with 2-(diphenylphosphanyl)-4-fluorophenyl esters to afford α- and β-N-glycosyl amino acids is described. The ligation method works reliably well for unprotected β-azides of the gluco, galacto and fuco series. Lower yields (ca. 50 %) were obtained with a β-glucosyl-N-acetyl azide. The reaction of an α-glucosyl azide also led to

  描述了未保护的α-和β-糖基叠氮化物与2-(二苯基膦酰基)-4-氟苯基酯的立体保守施陶丁格结扎，以提供α-和β-N-糖基氨基酸。对于葡糖、半乳糖和岩藻糖系列的未受保护的 β-叠氮化物，连接方法非常可靠。使用 β-葡萄糖基-N-乙酰叠氮化物获得较低的产率（约 50%）。与使用非氟化膦相比，α-葡萄糖基叠氮化物的反应也带来了重大改进。所有 N-糖基氨基酸产物都可以通过简单的水萃取从粗反应混合物中分离和去除副产物。 (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
• Traceless Staudinger Ligation of Glycosyl Azides with Triaryl Phosphines:  Stereoselective Synthesis of Glycosyl Amides
  作者：Aldo Bianchi、Anna Bernardi

  DOI：10.1021/jo060409s

  日期：2006.6.1

  α-Glycosyl amides can be synthesized from the corresponding O-benzyl-α-glycosyl azides using a traceless Staudinger ligation with diphenylphosphanyl-phenyl esters 4. All the phosphines employed and their phenol precursors are stable to air at 4 °C for months. Fast intramolecular trapping of the reduction intermediates results in the direct formation of the amide link, which, in turn, prevents epimerisation

  α-糖基酰胺可通过无痕施陶丁格与二苯基膦酰基-苯基酯的连接由相应的O-苄基-α-糖基叠氮化物合成4。所用的所有膦及其苯酚前体在4°C的空气中均可保持稳定数月。还原中间体的快速分子内捕集导致酰胺键的直接形成，继而防止了差向异构化并允许在异头碳上保留构型。当反应在极性非质子溶剂中进行时，产率和α-选择性高。苄基醚保护基的去除是通过催化氢化来实现的。α-糖基酰胺代表了一类实际上未开发的不可水解的单糖衍生物，可以作为糖模拟物找到有用的应用。NMR光谱的构象研究证实，葡萄糖，半乳糖和fuco系列中的脱保护α-糖基酰胺保留了单糖的正常吡喃糖构象。膦的反应4用四ø -乙酰基葡糖基叠氮化物是nonstereoconservative，并在良好的产率，并与来自两个α和β叠氮化物开始完整的立体选择性获得β糖基酰胺。
• Cu-Catalyzed Formation of Triazole-Linked Glycoamino Acids and Application in Chemoenzymatic Peptide Synthesis
  作者：Brian H. M. Kuijpers、Stan Groothuys、Christine Hawner、Jeroen ten Dam、Peter J. L. M. Quaedflieg、Hans E. Schoemaker、Floris L. van Delft、Floris P. J. T. Rutjes

  DOI：10.1021/op700249f

  日期：2008.5.1

  Novel stable triazole-linked glycoamino acids have been prepared, with the heterocyclic moiety being established by efficient Cu-mediated cycloaddition between the corresponding azido and acetylene moieties. Selected reactions were scaled up and successfully subjected to chemoenzymatic peptide-coupling reactions involving the proteolytic enzyme alcalase, resulting in several glycosylated di- and tripeptide structures. Since chemoenzymatic approaches have several advantages over chemical peptide coupling, especially concerning large-scale peptide synthesis, these results may be regarded as initial steps in the direction of production via fully chemoenzymatic peptide synthesis.