N-α-9-fluorenylmethoxycarbonyl-N-β-(β-D-glucopyranosyl)-L-asparagine tert-butyl ester | 887002-95-1

• 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-9-fluorenylmethoxycarbonyl-N-β-(β-D-glucopyranosyl)-L-asparagine tert-butyl ester
• 英文别名: Fmoc-Asn(Glc)-OtBu；tert-butyl (2S)-2-(9H-fluoren-9-ylmethoxycarbonylamino)-4-oxo-4-[[(2R,3R,4S,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]amino]butanoate
• CAS: 887002-95-1
• 化学式: C₂₉H₃₆N₂O₁₀
• 分子量: 572.612
• InChiKey: ZUTBUNDIRGKULK-CAMKMCDZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  41
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  184
• 氢给体数：
  6
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  N-α-9-fluorenylmethoxycarbonyl-N-β-(β-D-glucopyranosyl)-L-asparagine tert-butyl ester 在 三氟乙酸 作用下， 反应 0.25h， 生成 Fmoc-Asn(Glc)-OH
  参考文献：
  名称：

  Solid-phase synthesis of glycopeptides: synthesis of Nα-Flourenylmethoxycarbonyl L-asparagine Nβ-glycosides

  摘要：

  It was found that crude 1-glycosylamines, prepared with saturated aqueous NH4HCO3 from reducing sugars, can be coupled with Fmoc-Asp(OPfp)-O(t)Bu in N,N-dimethylformamide-water mixtures. Purification and removal of the (t)Bu group results in N-beta-glycosides of Fmoc-Asn-OH which can be used for the solid phase synthesis of glycopeptides.

  DOI：

  10.1016/0040-4039(91)80802-d
• 作为产物：
  描述：

  可得然胶 在 碳酸氢铵 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 148.0h， 生成 N-α-9-fluorenylmethoxycarbonyl-N-β-(β-D-glucopyranosyl)-L-asparagine tert-butyl ester
  参考文献：
  名称：

  Solid-phase synthesis of glycopeptides: synthesis of Nα-Flourenylmethoxycarbonyl L-asparagine Nβ-glycosides

  摘要：

  It was found that crude 1-glycosylamines, prepared with saturated aqueous NH4HCO3 from reducing sugars, can be coupled with Fmoc-Asp(OPfp)-O(t)Bu in N,N-dimethylformamide-water mixtures. Purification and removal of the (t)Bu group results in N-beta-glycosides of Fmoc-Asn-OH which can be used for the solid phase synthesis of glycopeptides.

  DOI：

  10.1016/0040-4039(91)80802-d

文献信息

• Chemoselective coupling of sugar oximes and α-ketoacids to glycosyl amides and N-glycopeptides
  作者：Claudia Pöhner、Vera Ullmann、Ramona Hilpert、Eric Samain、Carlo Unverzagt

  DOI：10.1016/j.tetlet.2014.02.056

  日期：2014.4

  The reaction of unprotected sugar hydroxylamines and oximes with α-ketoacids leads to the chemoselective formation of glycosyl amides following the decarboxylative condensation pathway of Bode’s ketoacid hydroxylamine (KAHA) ligation. Sugar oximes with gluco configuration stereoselectively form β-linked products. This method can be used for the convergent synthesis of N-acylated sugars and oligosaccharides

  未保护的糖羟胺和肟与α-酮酸的反应会导致Bode酮酸羟胺（KAHA）的脱羧缩合路径发生化学选择性的糖基酰胺形成。具有葡萄糖构型的糖肟立体选择性地形成β-连接的产物。该方法可用于收敛合成在酰基部分带有小标记，间隔基或肽的N-酰化糖和寡糖。
• Novel sequential solid-phase synthesis of N-linked glycopeptides from natural sources
  作者：Ernst Meinjohanns、Morten Meldal、Hans Paulsen、Raymond A. Dwek、Klaus Bock

  DOI：10.1039/a705528e

  日期：——

  In the present report a practical and versatile procedure for the solid-phase synthesis of N-linked glycopeptides from natural sources has been demonstrated. The approach is based on the mild hydrazinolysis procedure to release N-linked oligosaccharides in their intact unreduced form from the natural glycoproteins, e.g. fetuin and ribonuclease B and subsequent formation of the corresponding glycosylamines. Treatment of the reducing sugars 1–7 with a saturated solution of ammonium hydrogen carbonate in either water or dimethyl sulfoxide (DMSO) gives in almost quantitative yields the glycosylamines 8–14. Coupling of the unprotected glycosylamines 8–14 to the side-chain-activated aspartic acid derivative Fmoc-Asp(ODhbt)-OBut 16 affords the N-glycosylated asparagine derivatives 17–23. Subsequent acetylation of the carbohydrate hydroxy groups and cleavage of the tert-Bu ester by trifluoroacetic acid (TFA) treatment yields the glycosylated N-linked building blocks 31–37. The building blocks 31–37 are then incorporated into the multiple-column peptide-synthesis protocol of the glycopeptide T-cell epitope analogues 40–46 of the mouse haemoglobin-derived decapeptide Hb (67–76), VITAFNEGLK. The decapeptide sequence VITAFNEGLK binds well to the MHC Class II Ek molecule and is non-immunogenic in CBA/J mice. Syntheses of several natural and unnatural glycosylations, e.g. N-acetylglucosamine, N,N′-diacetylchitobiose, glucose, maltotriose, maltoheptose and di- and tri-antennary complex oligosaccharides on the decapeptide Hb (67–76) affording the N-linked glycopeptides 40–46 are described. The N-linked glycopeptides 40–46 have been fully characterised by 1D- and 2D-1H and 13C NMR spectroscopy and by ES-MS.

  本报告展示了一种从天然来源固相合成 N-连接糖肽的实用且多功能的方法。该方法基于温和的肼解程序，以完整的未还原形式从天然糖蛋白（如胎盘素和核糖核酸酶 B）中释放出 N-连接寡糖，随后形成相应的糖基胺。用碳酸氢铵在水或二甲基亚砜（DMSO）中的饱和溶液处理还原糖 1-7，几乎可以得到定量的糖基胺 8-14。将未受保护的糖基胺 8-14 与侧链激活的天冬氨酸衍生物 Fmoc-Asp(ODhbt)-OBut 16 偶联，可得到 N-糖基化的天冬酰胺衍生物 17-23。随后通过三氟乙酸（TFA）处理对碳水化合物羟基进行乙酰化并裂解叔丁酯，可得到糖基化的 N-连接构筑模块 31-37。然后，将这些结构单元 31-37 加入小鼠血红蛋白衍生的十肽 Hb（67-76）VITAFNEGLK 的糖肽 T 细胞表位类似物 40-46 的多柱肽合成方案中。十肽序列 VITAFNEGLK 与 MHC II 类 Ek 分子结合良好，对 CBA/J 小鼠无免疫原性。本文介绍了在十肽 Hb（67-76）上进行几种天然和非天然糖基化，如 N-乙酰葡糖胺、N,N′-二乙酰壳寡糖、葡萄糖、麦芽三糖、麦芽庚糖以及二元和三元泛酰复合寡糖，从而得到 N-连接的糖肽 40-46。通过 1D- 和 2D-1H 和 13C NMR 光谱以及 ES-MS 对 N-连接的糖肽 40-46 进行了全面鉴定。
• Direct deprotected glycosyl–asparagine ligation
  作者：Katie J. Doores、Yusuke Mimura、Raymond A. Dwek、Pauline M. Rudd、Tim Elliott、Benjamin G. Davis

  DOI：10.1039/b515472c

  日期：——

  A simple and efficient synthesis of N-linked glycoamino acids and glycopeptides from deprotected sugars using the Staudinger reaction.

  使用施陶丁格反应从脱保护的糖中简单高效地合成 N-连接糖氨基酸和糖肽。
• Solid-phase synthesis of glycopeptides: synthesis of Nα-Flourenylmethoxycarbonyl L-asparagine Nβ-glycosides
  作者：Laszlo Urge、Emma Kollat、Miklos Hollosi、Ilona Laczko、Krzysztof Wroblewski、Jan Thurin、Laszlo Otvos

  DOI：10.1016/0040-4039(91)80802-d

  日期：1991.7

  It was found that crude 1-glycosylamines, prepared with saturated aqueous NH4HCO3 from reducing sugars, can be coupled with Fmoc-Asp(OPfp)-O(t)Bu in N,N-dimethylformamide-water mixtures. Purification and removal of the (t)Bu group results in N-beta-glycosides of Fmoc-Asn-OH which can be used for the solid phase synthesis of glycopeptides.