allyl N⁴-[2-acetamido-2-deoxy-4-O-(2-acetamido-2-deoxy-3,4,6-tri-O-tert-butyldimethylsilyl-β-D-glucopyranosyl)-3,6-di-O-tert-butyldimethylsilyl-β-D-glucopyranosyl]-N²-(fluoren-9-ylmethyloxycarbonyl)-L-aspartate | 214489-87-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: allyl N⁴-[2-acetamido-2-deoxy-4-O-(2-acetamido-2-deoxy-3,4,6-tri-O-tert-butyldimethylsilyl-β-D-glucopyranosyl)-3,6-di-O-tert-butyldimethylsilyl-β-D-glucopyranosyl]-N²-(fluoren-9-ylmethyloxycarbonyl)-L-aspartate
• 英文别名: allyl-N⁴-[2-acetamido-2-deoxy-4-O-(2-acetamido-2-deoxy-3,4,6-tri-O-tert-butyldimethylsilyl-β-D-glucopyranosyl)-3,6-di-O-tert-butyldimethylsilyl-β-D-glucopyranosyl]-N²-(fluoren-9-ylmethyloxycarbonyl)-L-aspartate；allyl N⁴-[2-acetamido-2-deoxy-4-O-(2-acetamido-2-deoxy-3,4,6-tri-O-tert-butyldimethylsilyl-β-D-glucopyranosyl)-3,6-di-O-tert-butyldimethylsilyl-β-D-glucopyranosyl]-N²-(fluoren-9-ylmethoxycarbonyl)-L-aspartate；prop-2-enyl (2S)-4-[[(2R,3R,4R,5R,6R)-3-acetamido-5-[(2S,3R,4R,5R,6R)-3-acetamido-4,5-bis[[tert-butyl(dimethyl)silyl]oxy]-6-[[tert-butyl(dimethyl)silyl]oxymethyl]oxan-2-yl]oxy-4-[tert-butyl(dimethyl)silyl]oxy-6-[[tert-butyl(dimethyl)silyl]oxymethyl]oxan-2-yl]amino]-2-(9H-fluoren-9-ylmethoxycarbonylamino)-4-oxobutanoate
• CAS: 214489-87-9
• 化学式: C₆₈H₁₁₈N₄O₁₅Si₅
• 分子量: 1372.13
• InChiKey: ZHLOAIVINOCCPB-PAXLYCSZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.19
• 重原子数：
  92
• 可旋转键数：
  32
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  226
• 氢给体数：
  4
• 氢受体数：
  15

反应信息

• 作为反应物：
  描述：

  allyl N⁴-[2-acetamido-2-deoxy-4-O-(2-acetamido-2-deoxy-3,4,6-tri-O-tert-butyldimethylsilyl-β-D-glucopyranosyl)-3,6-di-O-tert-butyldimethylsilyl-β-D-glucopyranosyl]-N²-(fluoren-9-ylmethyloxycarbonyl)-L-aspartate 在 四(三苯基膦)钯 、 苯硅烷 作用下， 以 二氯甲烷 为溶剂， 生成 N⁴-[2-acetamido-2-deoxy-4-O-(2-acetamido-2-deoxy-3,4,6-tri-O-tert-butyldimethylsilyl-β-D-glucopyranosyl)-3,6-di-O-tert-butyldimethylsilyl-β-D-glucopyranosyl]-N²-(fluoren-9-ylmethyloxycarbonyl)-L-aspartic acid
  参考文献：
  名称：

  立体选择性合成β-连接的TBDMS保护的壳二糖-天冬酰胺：淀粉样蛋白生成糖肽的通用构建基块

  摘要：

  描述了一种对β-连接的碳水化合物具有选择性的Fmoc-1-Asn [β-壳二糖（TBDMS）5 ] -OH的简单有效的合成方法。在代表小鼠病毒蛋白（PrPGP）的175-195 †片段的糖基化淀粉样蛋白生成肽的合成中说明了此构件的实用性。

  DOI：

  10.1016/s0040-4039(01)01524-6
• 作为产物：
  描述：

  N,N'-Diacetylchitobiose 在 吡啶 、 4-二甲氨基吡啶 、 ammonium carbamate 、 1-羟基苯并三唑 、 O-(1H-benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate 、 N,N-二异丙基乙胺 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 48.0h， 生成 allyl N⁴-[2-acetamido-2-deoxy-4-O-(2-acetamido-2-deoxy-3,4,6-tri-O-tert-butyldimethylsilyl-β-D-glucopyranosyl)-3,6-di-O-tert-butyldimethylsilyl-β-D-glucopyranosyl]-N²-(fluoren-9-ylmethyloxycarbonyl)-L-aspartate
  参考文献：
  名称：

  Improving Glycopeptide Synthesis:  A Convenient Protocol for the Preparation of β-Glycosylamines and the Synthesis of Glycopeptides

  摘要：

  Herein we apply a recently introduced protocol using ammonium carbamate in methanol to the amination of crude chitobiose leading to 1,beta-aminochitobiose. This simple, one-step procedure allows a facile preparation of unstable glycosylamines in contrast to the commonly implemented ammonium bicarbonate based amination of water-soluble carbohydrates. The new amination protocol leads to an improved synthesis of the key chitobiosyl-asparagine building block for the SPPS of glycopeptides. The utility of the method is demonstrated with the synthesis of a 39-amino acid glycoprotein.

  DOI：

  10.1021/jo047801v

文献信息

• Effects of Glycosylation on Peptide Conformation:  A Synergistic Experimental and Computational Study
  作者：Carlos J. Bosques、Sarah M. Tschampel、Robert J. Woods、Barbara Imperiali

  DOI：10.1021/ja0496266

  日期：2004.7.14

  glycosylation, the co-translational covalent attachment of carbohydrates to asparagine side chains, has a major effect on the folding, stability, and function of many proteins. The carbohydrate composition in mature glycoproteins is heterogeneous due to modification of the initial oligosaccharide by glycosidases and glycosyltransferases during the glycoprotein passage through the endoplasmic reticulum and Golgi

  天冬酰胺连接的糖基化，即碳水化合物与天冬酰胺侧链的共翻译共价连接，对许多蛋白质的折叠、稳定性和功能有重大影响。由于糖蛋白通过内质网和高尔基体期间糖苷酶和糖基转移酶对初始寡糖的修饰，成熟糖蛋白中的碳水化合物组成是异质的。尽管碳水化合物结构的多样性，核心 beta-D-(GlcNAc)(2) 在所有 N 连接的糖蛋白中仍然保守。此前，我们实验室的结果表明，核心二糖的分子组成对肽主链具有关键且独特的构象影响。在此处，我们采用协同实验和计算方法来研究碳水化合物-肽键的立体化学对糖肽结构的影响。合成了源自血凝素蛋白片段的糖肽，其中碳水化合物通过α-连接的立体化学连接到肽上。计算和生物物理分析表明，肽和 α 和 β 连接的糖肽的构象受到所附糖的独特影响。突出了用于探测附着的糖对多肽构象影响的计算方法的价值。碳水化合物通过α-连接的立体化学连接到肽上。计算和生物物理分析表明，肽和 α 和 β 连接的糖肽
• Stereoselective synthesis of β-linked TBDMS-protected chitobiose-asparagine: a versatile building block for amyloidogenic glycopeptides
  作者：Carlos J Bosques、Vincent W.-F Tai、Barbara Imperiali

  DOI：10.1016/s0040-4039(01)01524-6

  日期：2001.10

  A simple and efficient synthesis of a Fmoc-l-Asn[β-chitobiose(TBDMS)5]-OH with selectivity for the β-linked carbohydrate is described. The utility of this building block is illustrated in the synthesis of a glycosylated amyloidogenic peptide representing the 175-195† fragment of the mouse prion protein (PrPGP).

  描述了一种对β-连接的碳水化合物具有选择性的Fmoc-1-Asn [β-壳二糖（TBDMS）5 ] -OH的简单有效的合成方法。在代表小鼠病毒蛋白（PrPGP）的175-195 †片段的糖基化淀粉样蛋白生成肽的合成中说明了此构件的实用性。
• Synthesis of an N-linked glycopeptide from vitamin K-dependent protein S
  作者：Björn Holm、Sara Linse、Jan Kihlberg

  DOI：10.1016/s0040-4020(98)83053-6

  日期：1998.9

  protected with acid-labile TBDMS groups has been prepared. The building block was used in Fmoc solid-phase synthesis of a glycopeptide fragment corresponding to residues 447–460 of protein S which has a potential N-glycosylation site at Asn458. The TBDMS groups of the chitobiose moiety were removed during cleavage of the glycopeptide from the solid phase, thus simplifying synthesis as compared to when using

  已经制备了具有用酸不稳定的TBDMS基团保护的N-连接的壳二糖部分的新型天冬酰胺结构单元。该构造块用于Fmoc固相合成糖肽片段，该片段对应于蛋白S的447-460残基，该残基在Asn 458上具有潜在的N-糖基化位点。在从固相切割糖肽的过程中，壳二糖部分的TBDMS基团被除去，因此与对碳水化合物使用乙酰基保护时相比，简化了合成过程。蛋白S是一种抗凝剂，可以通过C4b结合蛋白（C4BP）的复合作用而失活。发现蛋白S 447-460糖肽比非糖基化的亲本肽是更有效的复合物形成抑制剂，表明蛋白S可能在Asn 458带有N-连接的聚糖。
• Improving Glycopeptide Synthesis:  A Convenient Protocol for the Preparation of β-Glycosylamines and the Synthesis of Glycopeptides
  作者：Christian P. R. Hackenberger、Mary K. O'Reill、Barbara Imperiali

  DOI：10.1021/jo047801v

  日期：2005.4.1

  Herein we apply a recently introduced protocol using ammonium carbamate in methanol to the amination of crude chitobiose leading to 1,beta-aminochitobiose. This simple, one-step procedure allows a facile preparation of unstable glycosylamines in contrast to the commonly implemented ammonium bicarbonate based amination of water-soluble carbohydrates. The new amination protocol leads to an improved synthesis of the key chitobiosyl-asparagine building block for the SPPS of glycopeptides. The utility of the method is demonstrated with the synthesis of a 39-amino acid glycoprotein.