O-(2,3,4-tri-O-acetyl-6-azido-6-deoxy-α-D-glucopyranosyl)trichloroacetimidate | 191668-79-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: O-(2,3,4-tri-O-acetyl-6-azido-6-deoxy-α-D-glucopyranosyl)trichloroacetimidate
• 英文别名: 2,3,4-tri-O-acetyl-6-azido-6-deoxy-α-D-glucopyranosyl trichloroacetimidate；6-azido-2,3,4-tri-O-acetyl-6-deoxy-α-D-glucopyranosyl trichloroacetimidate；2,3,4-tri-O-acetyl-6-azido-6-deoxy-D-glucopyranosyl trichloroacetimidate；[(2R,3R,4S,5R,6R)-4,5-diacetyloxy-2-(azidomethyl)-6-(2,2,2-trichloroethanimidoyl)oxyoxan-3-yl] acetate
• CAS: 191668-79-8
• 化学式: C₁₄H₁₇Cl₃N₄O₈
• 分子量: 475.67
• InChiKey: BLXLRJMPROSYSS-RMPHRYRLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  29
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  136
• 氢给体数：
  1
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  O-(2,3,4-tri-O-acetyl-6-azido-6-deoxy-α-D-glucopyranosyl)trichloroacetimidate 在 氨 、 copper(II) sulfate 、 sodium ascorbate 作用下， 以 1,4-二氧六环 、 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 25.25h， 生成 (2S,3R,4S,5S,6R)-2-(2-aminoethylsulfanyl)-6-[[4-[7-[(2S,3S,4S,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyheptoxymethyl]triazol-1-yl]methyl]oxane-3,4,5-triol
  参考文献：
  名称：

  通过使用具有碳水化合物核心的多聚庚基α-D-甘露糖苷探针对大肠杆菌1型纤维粘附素进行聚类

  摘要：

  庚基α- D-甘露糖苷（HM）是FimH凝集素的强抑制剂，可介导尿路致病性大肠杆菌（E. coli）的初始黏附）到膀胱细胞。我们基于碳水化合物核设计了一组多价HM配体，结构化合价范围为1到7。用于构建规则亲水结构的化学策略包括关键糖苷片段的重复。伯氨基在糖还原端接枝以将多聚体偶联至荧光标记。开发了一种单锅合成方法，可将配体和异硫氰酸荧光素（FITC）探针同时束缚到支架上。用单体FimH凝集素等温量热法显示纳摩尔亲和力和多价HM配体上所有结构上可用的结合位点饱和。直接滴定域显示出焓-熵补偿与配体价的增加几乎严格相关，而反向滴定量热法则表明二价庚基甘露糖苷的第一个和第二个结合位点之间存在负协同作用。但是，通过抑制1型毛细血管UTI89的血凝作用，观察到了多价效应。大肠杆菌，具有滴度低到60牛顿中号为七价HM配体。FITC标记的HM三聚体显示了溶液中活细菌的捕获和交联，这种现象以前没有用低价配体描述。

  DOI：

  10.1002/chem.201100515
• 作为产物：
  描述：

  methyl 2,3-O-dibenzyl-4,6-O-benzylidene-α-D-glucopyranoside 在 吡啶 、 sodium azide 、 硫酸 、 乙酸肼 、 对甲苯磺酸 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 O-(2,3,4-tri-O-acetyl-6-azido-6-deoxy-α-D-glucopyranosyl)trichloroacetimidate
  参考文献：
  名称：

  Application of the Synthetic Aminosugars for Glycodiversification:  Synthesis and Antimicrobial Studies of Pyranmycin

  摘要：

  A divergent approach was employed for the synthesis of aminosugars, from which a novel library of aminoglycoside antibiotics (pyranmycins) was synthesized. Pyranmycins have comparable antibacterial activity as neomycin, a clinically used aminoglycoside antibiotic, against Escherichia coli, Staphylococcus aureus, Bacillus subtilis, and Mycobacterium smegmatis. In addition, pyranmycins, like streptomycin, are bacteriocidal while isoniazid (INH) is bacteriostatic. Therefore, pyranmycins may provide new therapeutic options in the treatment against tuberculosis. Several members of pyranmycins also manifest modest anti-Tat and anti-Rev activities, which may aid in the development of new anti-HIV agents. Although the antibacterial activity of pyranmycins against aminoglycoside resistant bacteria is less than expected, the synthetic methodologies of utilizing a library of aminosugars can be a model for future studies of glycodiversification or glycorandomization.

  DOI：

  10.1021/jo035290r

文献信息

• Synthesis of Hetero-bifunctional Azobenzene Glycoconjugates for Bioorthogonal Cross-Linking of Proteins
  作者：Anne Müller、Thisbe K. Lindhorst

  DOI：10.1002/ejoc.201600136

  日期：2016.3

  Modification of proteins with azobenzene derivatives allows their form and function to be controlled by photochemical E/Z isomerization of the azobenzene N=N bond. Because azobenzene glycoconjugates (ABGs) are particularly promising cross-linkers for the modification of peptides and proteins, we advanced the collection of so far known homo-bifunctional ABGs with the synthesis of hitherto unknown h

  用偶氮苯衍生物修饰蛋白质可以通过偶氮苯 N=N 键的光化学 E/Z 异构化来控制它们的形式和功能。由于偶氮苯糖缀合物 (ABG) 是用于修饰肽和蛋白质的特别有前途的交联剂，因此我们通过合成迄今为止未知的异双功能 ABG，推进了迄今为止已知的同双功能 ABG 的收集。炔烃和烯烃、炔烃和巯基、叠氮基和烯烃官能团结合在一个分子中，作为生物正交反应对。有了这个，提供了对大量光敏蛋白的访问。
• A hydrophobic disordered peptide spontaneously anchors a covalently bound RNA hairpin to giant lipidic vesicles
  作者：Alexandra Le Chevalier Isaad、Paolo Carrara、Pasquale Stano、Kollappillil S. Krishnakumar、Dominique Lafont、Alexandra Zamboulis、René Buchet、Denis Bouchu、Florian Albrieux、Peter Strazewski

  DOI：10.1039/c4ob00721b

  日期：——

  Exergonic compartmentation of nucleic acids to liposomes through conjugation with peptides lends experimental support to early evolvable RNA–peptide ‘collaboration’.

  核酸通过与肽共轭形成脂质体的外源性分隔，为早期可进化的RNA-肽“协作”提供了实验支持。
• Internally quenched fluorogenic, α-helical dimeric peptides and glycopeptides for the evaluation of the effect of glycosylation on the conformation of peptides
  作者：Seema Mehta、Morten Meldal、Vito Ferro、Jens Ø. Duus、Klaus Bock

  DOI：10.1039/a607624f

  日期：——

  A panel of α-helical, dimeric coiled-coil peptides has been designed and synthesized for the evaluation of the effect of glycosylation on the conformation of these coiled-coil peptides. Two glycosylated building blocks, Nα -(fluoren-9-ylmethoxycarbonyl)-O-(2,3,4-tri- O-acetyl-6-azido-6-deoxy-β-D -glucopyranosyl)-L-threonine pentafluorophenyl ester 8 and Nα -(fluoren-9-ylmethoxycarbonyl)-O-2,3,4-tri- O-acetyl-6-[2′-(tert -butoxycarbonylamino)benzoylamino]-6-deoxy-β-D -glucopyranosyl}-L-threonine pentafluorophenyl ester 9 containing the fluorogenic 2-aminobenzamide (Abz) group, have been synthesized. These compounds have been obtained by the glycosylation of Nα-Fmoc-Thr-OPfp with the corresponding glycosyl trichloroacetimidate donors and have been incorporated into the solid-phase synthesis of the peptides 1–3 and 7 and glycopeptides 4–6. Compounds 1 and 4–7 have been synthesized as internally quenched fluorogenic compounds where the Abz group has been employed as the fluorogenic probe and 3-nitrotyrosine Tyr(NO2) as the quenching chromophore. Steady-state fluorescence studies have provided evidence to support the dimerization of the α-helical peptides. Denaturation studies, by fluorescence as well as CD spectroscopy, indicate that the introduction of a carbohydrate moiety into the coiled-coil peptides has a significant destabilizing effect on the α-helicity.

  设计并合成了一组α-螺旋二聚体缠绕螺旋肽，以评估糖基化对这些缠绕螺旋肽构象的影响。合成了两个糖基化构建块，Nα-(荧光-9-基甲氧基碳酰基)-O-(2,3,4-三-O-乙酰-6-氮化-6-脱氧-β-D-葡萄糖吡喃糖)-L-苏氨酸五氟苯酯8和Nα-(荧光-9-基甲氧基碳酰基)-O-2,3,4-三-O-乙酰-6-[2'-(叔丁氧羰基氨基)苯甲酰氨基]-6-脱氧-β-D-葡萄糖吡喃糖}-L-苏氨酸五氟苯酯9，这些分子含有荧光基团2-氨基苯酰胺（Abz）。这些化合物是通过Nα-Fmoc-Thr-OPfp与相应的糖基三氯乙酰亚胺供体糖基化而获得的，并已整合到肽1-3和7以及糖肽4-6的固相合成中。化合物1和4-7被合成为内部猝灭荧光化合物，其中Abz基团作为荧光探针，3-硝基酪氨酸Tyr(NO2)作为猝灭颜料。稳态荧光研究提供了支持α-螺旋肽二聚化的证据。荧光及圆二色谱的变性研究表明，向缠绕螺旋肽中引入糖类基团对α-螺旋的稳定性有显著的破坏作用。
• Photocontrol over Molecular Shape: Synthesis and Photochemical Evaluation of Glycoazobenzene Macrocycles
  作者：Guillaume Despras、Julia Hain、Sven Ole Jaeschke

  DOI：10.1002/chem.201701232

  日期：2017.8.10

  external stimuli is an attractive property for the control of molecular features. Hence, we aimed at macrocycles to investigate photoswitching of molecular shape. We prepared the first carbohydrate-based macrocycles comprising a photoresponsive azobenzene hinge. These macrocycles were readily obtained by cyclization of isothiocyanate-armed bis-azobenzene glycosides with piperazine. The unprotected macrocycles

  由于外部刺激而引起的可逆形状转换是控制分子特征的诱人特性。因此，我们针对大环研究分子形状的光开关。我们制备了包含光响应性偶氮苯铰链的第一个基于碳水化合物的大环化合物。这些大环很容易通过哌嗪将异硫氰酸酯武装的双偶氮苯糖苷环化而获得。未保护的大环化合物在水和DMSO中表现出良好的光致变色特性。值得注意的是，有效的反式顺式异构化导致分子的显着形状转变。此外，该结构的特征是骨架的构象自由受到限制，导致每个几何状态（反式或cis）。旋光度值和圆二色性光谱的测量结果表明，光异构化后手性发生了巨大变化，顺式状态下有很强的螺旋感应。这些发现突出了新的大环化合物作为手性分子开关的适用性。
• Synthetic Glycosphingolipids for Live-Cell Labeling
  作者：Martin Dauner、Ellen Batroff、Verena Bachmann、Christof R. Hauck、Valentin Wittmann

  DOI：10.1021/acs.bioconjchem.6b00177

  日期：2016.7.20

  insight into their localization. However, the attachment of a fluorophore to the glycan part or - more commonly - to the lipid part of glycosphingolipids is known to alter the biophysical properties and can perturb the biological function of the probe. Presented here is the synthesis of novel glycosphingolipid probes with mono and disaccharide head groups and ceramide moieties containing fatty acids of varying

  糖鞘脂是涉及许多生物学过程的细胞膜的重要组成部分。荧光标记的糖鞘脂经常用于深入了解其定位。然而，已知荧光团与糖鞘脂的聚糖部分或更通常地与脂质部分的附着会改变生物物理特性，并且会干扰探针的生物学功能。本文介绍的是具有单糖和二糖首基以及神经酰胺部分的新型糖鞘脂探针的合成，所述神经酰胺部分含有链长不同的脂肪酸（C4至C20）。这些糖鞘脂具有作为化学报告基的叠氮基或炔基，可以通过生物正交连接反应将荧光团连接至其上。可以以灵活的方式选择荧光标签和与其连接的任何接头。我们通过共聚焦显微镜技术选择性观察活细胞的质膜，证明了探针的适用性。具有较短脂肪酸的衍生物可直接应用于HEK 293T细胞，而具有较长脂肪酸的疏水性鞘糖脂可使用融合脂质体递送至细胞。