6,6'-二叠氮基-6,6'-二脱氧-Α,Α-D-海藻糖六乙酸酯 | 23103-34-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 中文名称: 6,6'-二叠氮基-6,6'-二脱氧-Α,Α-D-海藻糖六乙酸酯
• 英文名称: 2,3,4,2',3',4'-hexa-O-acetyl-6,6'-diazido-6,6'-dideoxy-α,α'-trehalose
• 英文别名: 1,1'-Oxybis(6-azido-1,6-dideoxy-alpha-D-glucopyranose 2,3,4-triacetate)；[(2R,3R,4S,5R,6R)-4,5-diacetyloxy-2-(azidomethyl)-6-[(2R,3R,4S,5R,6R)-3,4,5-triacetyloxy-6-(azidomethyl)oxan-2-yl]oxyoxan-3-yl] acetate
• CAS: 23103-34-6
• 化学式: C₂₄H₃₂N₆O₁₅
• 分子量: 644.549
• InChiKey: NHOXHUUFWNGYEN-FXPCSOOLSA-N

物化性质

• 熔点：
  114-116 °C(Solv: methanol (67-56-1))

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  45
• 可旋转键数：
  18
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  214
• 氢给体数：
  0
• 氢受体数：
  19

反应信息

• 作为反应物：
  描述：

  6,6'-二叠氮基-6,6'-二脱氧-Α,Α-D-海藻糖六乙酸酯 在 吡啶 、 三苯基膦 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 1.0h， 生成 2,2',3,3'tetra-O-acetyl-6,6'-bis(N-acetylamino)-6,6'-deoxy-α,α'-trehalose
  参考文献：
  名称：

  Supramolecular structures of substituted α,α′-trehalose derivatives

  摘要：

  我们确定了五种取代的 α,α′-三卤糖三卤糖衍生物的结构，并将其与之前发表的四种类似物的结构进行了比较。在 2,2′,3,3′,4,4′-六乙酰氧基-6,6′-双-O-甲基磺酰基-α,α′-三卤糖 C26H38O21S2 中，分子位于空间群 C2 的两倍旋转轴上，一个 C-H...O=S 氢键将分子连接成片状。2,2′,3,3′,4,4′-六乙酰-6,6′-双-O-（4-甲苯磺酰）-α,α′-三卤糖，C38H46O21S2，在空间群 P212121 中以 Z′ = 2 结晶，由三个 C-H...O.氢键组合而成。...O氢键（每个氢键都有一个羰基O原子作为受体）和一个C-H...π（芴）氢键将分子连接成一个三维框架。2,2′,3,3′,4,4′-六乙酰-6,6′-叠氮-α,α′-三卤糖 C24H32N6O15 结晶为部分乙醇溶解物，三个 C-H...O 氢键将取代的三卤糖分子连接成一个三维框架。在 2,2′,3,3′-四乙酰-6,6′-双（N-乙酰氨基）-α,α′-曲哈洛糖二水合物 C24H36N2O15-2H2O 中，取代的曲哈洛糖分子位于空间群 P21212 的两倍旋转轴上，通过 O-H...O 和 N-H...O 氢键的结合形成了一个三维框架。6,6′-diamino-α,α′-trehalose dihydrate（C12H24N2O9.2(H2O)）中的二氨基海藻糖分子横跨空间群 P43212 中的两个旋转轴：一个 O-H...N 氢键将海藻糖分子连接成片状，这些片状分子通过 O-H...O 氢键连接成一个三维框架。

  DOI：

  10.1107/s0108768104010912
• 作为产物：
  描述：

  海藻糖 在 吡啶 、 N-碘代丁二酰亚胺 、 sodium azide 、 三苯基膦 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 6,6'-二叠氮基-6,6'-二脱氧-Α,Α-D-海藻糖六乙酸酯
  参考文献：
  名称：

  Effects of Trehalose Polycation End-Group Functionalization on Plasmid DNA Uptake and Transfection

  摘要：

  In this study, we have synthesized six analogs of a trehalose-pentaethylenehexamine glycopolymer (Tr4) that contain (1A) adamantane, (1B) carboxy, (1C) alkynyl-oligoethyleneamine, (1D) azido trehalose, (1E) octyl, or (1F) oligoethyleneamine end groups and evaluated the effects of polymer end group chemistry on the ability of these systems to bind, compact, and deliver pDNA to cultured HeLa cells. The polymers were synthesized in one pot azide-alkyne cycloaddition reactions with an adaptation of the Carothers equation for step growth polymerization to produce a series of polymers with similar degrees of polymerization. An excess of end-capping monomer was added at the end of the polymerizations to maximize functionalization efficiency, which was evaluated with GPC, NMR, and MALDI-TOF. The polymers were all found to bind and compact pDNA at similarly low N/P ratios and form polyplexes with plasmid DNA. The effects of the different end group structures were most evident in the polyplex internalization and transfection assays in the presence of serum as determined by flow cytometry and luciferase gene expression, respectively. The Tr4 polymers end capped with carboxyl groups (1B) (N/P = 7), octyne (1E) (N/P = 7), and oligoethyleneamine (1F) (N/P = 7), were taken into cells as polyplex and exhibited the highest levels of fluorescence, resulting from labeled plasmid. Similarly, the polymers end-functionalized with carboxyl groups (1E at N/P = 7), octyl groups (1E at N/P = 15), and in particular oligoethyleneamine groups (1F at N/P = 15) yielded dramatically higher reporter gene expression in the presence of serum. This study yields insight into how very subtle structural changes in polymer chemistry, such as end groups can yield very significant differences in the biological delivery efficiency and transgene expression of polymers used for pDNA delivery.

  DOI：

  10.1021/bm300471n

文献信息

• Synthesis of Per- and Poly-Substituted Trehalose Derivatives: Studies of Properties Relevant to Their Use as Excipients for Controlled Drug Release
  作者：Thomas C. Baddeley、James L. Wardell

  DOI：10.1080/07328300902887672

  日期：2009.5.22

  substituents, included 6,6′-N,N′ -diamido-6,6′ -dideoxy-α,α -trehalose derivatives, 6,6′ -bis(1,2,3,4-tetra-O-acetyl-β -D-glucopyranuronyl)-α, α -trehalose derivatives, 2,2′,3,3′ -tetra-O-acetyl-6,6′ -bis-(1,2,3,4-tetra-O-acetyl-β-D-glucopyranuronyl)-4,4′ -di-O-acyl-α,α-trehalose, 2, 2′, 3, 3′ -tetra-O-acetyl-6-(1,2,3,4-tetra-O-acetyl-β-D-glucopyranuronyl)-4,4′,6′ -tri-O-acyl-α,α-trehalose, and 2,2′,3,3′,4

  已经制备了具有海藻糖核心的全取代和多取代的寡糖衍生物，并评估了它们在控释制剂中用作赋形剂的潜力。通常具有酰基和酰胺基取代基的合成化合物包括6,6'- N，N'-二叠氮基-6,6'-二脱氧-α，α-海藻糖衍生物，6,6'-双（1,2,3） ，4-四-O-乙酰基-β-D-吡喃葡萄糖醛酸基）-α，α-海藻糖衍生物，2,2'，3,3'-四-O-乙酰基-6,6'-双-（1,2 ，3,4-四-O-乙酰基-β-D-吡喃葡萄糖醛酸）-4,4'-二-O-酰基-α，α-海藻糖，2，2'，3，3'-四-O-乙酰基-6-（1,2,3,4-四-O乙酰基β-d-glucopyranuronyl）-4,4'，6' -三ö酰基-α，α -海藻糖，和2,2'，3,3'，4,4'-hexa- ö -乙酰基-6,6'-双-（1,2,3,4-四-O-乙酰基-6- O-琥珀酰基-β-D-吡喃葡萄糖醛酸基）-α，α-海藻糖。用NMR
• A mild one-step selective conversion of primary hydroxyl groups into azides in mono- and oligo-saccharides
  作者：JoséLuis Jiménez Blanco、JoséManuel García Fernández、Andrée Gadelle、Jacques Defaye

  DOI：10.1016/s0008-6215(97)00176-6

  日期：1997.9

  tetrabromide is reported. The optimal reaction conditions require pre-formation of the reactive species before addition of the sugar substrate. Formation of the primary azidodeoxy compound is accompanied by simultaneous formation of the corresponding primary bromodeoxy and 3,6-anhydro derivatives in the glycopyranoside series, the former being transformed in situ into the azide by quenching of the reaction

  摘要报道了在三苯基膦碳四溴化物存在下，几种单糖甲基吡喃葡萄糖苷，蔗糖，α，α-海藻糖，环麦芽六糖和环麦芽七糖与叠氮化钠的直接叠氮化反应。最佳反应条件要求在添加糖底物之前预先形成反应性物质。伯叠氮基伯氧基化合物的形成伴随着糖吡喃糖苷系列中相应伯伯溴脱氧氧基和3,6-脱水衍生物的同时形成，通过在升高温度之前用甲醇淬灭反应混合物，将前者原位转化为叠氮化物。有趣的是，在蔗糖的情况下，与果糖呋喃糖基相比，对吡喃吡喃糖基部分的伯C-6位置具有良好的选择性，在改进的2,3,4,1'，3'，4'，6'-庚基-O-乙酰基-6-叠氮基-6-脱氧蔗糖的制备中获得了优势（蔗糖产率为45％）。发现叠氮化钠或叠氮化锂试剂同样有效。如先前对61-氨基-61-脱氧环麦芽七糖的制备所说明的，叠氮化物的官能度可以不经预先纯化而降低，并且所得的氨基糖通过阳离子交换柱色谱法分离。
• Synthesis of Multivalent Glycoclusters from 1-Thio-β-<scp>d</scp>-galactose and Their Inhibitory Activity against the β-Galactosidase from <i>E. coli</i>
  作者：Alejandro J. Cagnoni、Oscar Varela、Sébastien G. Gouin、José Kovensky、María Laura Uhrig

  DOI：10.1021/jo102421e

  日期：2011.5.6

  to 4 residues of 1-thio-β-d-galactose. The yields went from moderate to excellent, depending on the valency of the desired product. Deacetylation with Et3N/MeOH/H2O led to the final products. Complete characterization of the products was performed by NMR spectroscopy and HR-MS techniques. Their activities as inhibitors of β-galactosidase from E. coli were determined by using the Lineweaver−Burk method

  据报道，旨在与生物系统相容的多价糖簇的合成。已经合成了各种通过可变长度的低聚乙二醇链连接至末端三键的1-硫代-β- d-半乳糖苷。另外，通过用NaN 3 / PPh 3 / CBr 4直接叠氮化由海藻糖，麦芽糖和麦芽三糖制备含叠氮化物的寡糖支架。硫代半乳糖苷残基和叠氮化物支架之间在微波辐射下的点击反应提供了含有1-4个1-硫代-β- d-半乳糖残基的糖簇家族。取决于所需产品的化合价，收率从中等提高到极好。用Et脱乙酰3 N / MeOH / H 2 O生成最终产物。通过NMR光谱和HR-MS技术对产物进行完全表征。通过使用Lineweaver-Burk方法确定了它们作为大肠杆菌β-半乳糖苷酶抑制剂的活性。使用亲水性碳水化合物支架合成多价半乳糖苷代表了一种改善其药代动力学和生物利用度的有趣方法。另外，硫糖苷键的存在将改善它们在生物流体中的稳定性。
• Synthesis of divalent ligands of β-thio- and β-<i>N</i>-galactopyranosides and related lactosides and their evaluation as substrates and inhibitors of <i>Trypanosoma cruzi</i> trans-sialidase
  作者：María Emilia Cano、Rosalía Agusti、Alejandro J Cagnoni、María Florencia Tesoriero、José Kovensky、María Laura Uhrig、Rosa M de Lederkremer

  DOI：10.3762/bjoc.10.324

  日期：——

  ability of the different S-linked and N-linked glycosides to inhibit the sialic acid transfer reaction from 3'-sialyllactose to the natural substrate N-acetyllactosamine, was also studied. Most of the substrates behaved as good acceptors and moderate competitive inhibitors. A di-N-lactoside showed to be the strongest competitive inhibitor among the compounds tested (70% inhibition at equimolar concentration)

  在这项工作中，我们描述了在糖支架上构建的一价和二价β-N-和β-S-吡喃半乳糖苷和相关乳糖苷的合成及其作为锥虫锥虫唾液酸唾液酸酶（TcTS）的底物和抑制剂的评估。该酶催化唾液酸从宿主中的寡糖供体转移至寄生虫betaGalp末端单元，并且已证明其在感染中起重要作用。在本文中，还测试了该酶作为化学合成含唾液酸的糖簇的工具。在具有βGalp非还原端的受体的存在下，使用重组TcTS和3'-唾液乳糖作为唾液酸供体，进行唾液酸的转移反应。用高效阴离子交换色谱和脉冲安培检测法（HPAEC-PAD）对产物进行分析。还研究了不同的S-连接和N-连接的糖苷抑制唾液酸从3'-唾液乳糖向天然底物N-乙酰基乳糖胺转移的能力。大多数底物表现为良好的受体和中度竞争性抑制剂。在所测试的化合物中，二-N-乳糖苷显示出最强的竞争性抑制剂（在等摩尔浓度下抑制率为70％）。通过对二价底物进行制备性唾液酸化来评估酶促反唾液酸化用于
• Synthesis of β-galactosylamides as ligands of the peanut lectin. Insights into the recognition process
  作者：María Emilia Cano、Oscar Varela、María Isabel García-Moreno、José Manuel García Fernández、José Kovensky、María Laura Uhrig

  DOI：10.1016/j.carres.2017.03.018

  日期：2017.4

  to a hydroxylated chain having a C2 symmetry axis derived from l-tartaric anhydride is reported. Reference compounds devoid of hydroxyl groups in the linker were also prepared from β-galactosylamine and succinic anhydride. After functionalization with an alkynyl residue, the resulting building blocks were grafted onto different azide-equipped scaffolds through the copper catalyzed azide-alkyne cycloaddition

  报道了与衍生自1-酒石酸酐的具有C 2对称轴的羟基化链连接的一价和二价β-半乳糖酰胺的合成。还从β-半乳糖胺和琥珀酸酐制备了在接头中不含羟基的参考化合物。用炔基残基官能化后，通过铜催化的叠氮化物-炔烃环加成反应，将得到的结构单元接枝到不同的装有叠氮化物的支架上。因此，获得了一系列结构相关的单价和二价β-N-吡喃半乳糖苷酰胺，并对其进行了充分表征。通过酶联凝集素测定法（ELLA）测量配体对模型凝集素PNA的结合亲和力。IC50值明显高于半乳糖，但糖苷配基链中羟基的存在改善了凝集素的识别。对接和分子动力学实验符合以下假设：在识别过程中，正确放置在接头中的羟基可以模仿Glc O3。另一方面，配体的二价呈递导致凝集素亲和力增强。