6,6'-diazido-6,6'-dideoxy-α,α-trehalose | 18933-88-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6,6'-diazido-6,6'-dideoxy-α,α-trehalose
• 英文别名: (2R,3S,4S,5R,6R)-2-(azidomethyl)-6-[(2R,3R,4S,5S,6R)-6-(azidomethyl)-3,4,5-trihydroxy-tetrahydropyran-2-yl]oxy-tetrahydropyran-3,4,5-triol；(2R,3S,4S,5R,6R)-2-(azidomethyl)-6-[(2R,3R,4S,5S,6R)-6-(azidomethyl)-3,4,5-trihydroxyoxan-2-yl]oxyoxane-3,4,5-triol
• CAS: 18933-88-5
• 化学式: C₁₂H₂₀N₆O₉
• 分子量: 392.326
• InChiKey: SEOGZJSYAKUEQG-LIZSDCNHSA-N

物化性质

• 熔点：
  211 °C

计算性质

• 辛醇/水分配系数(LogP)：
  -2.1
• 重原子数：
  27
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  178
• 氢给体数：
  6
• 氢受体数：
  13

安全信息

• 储存条件：
  | 2-8°C |

反应信息

• 作为反应物：
  描述：

  6,6'-diazido-6,6'-dideoxy-α,α-trehalose 在 1,3-丙二硫醇 、 sodium tetrahydroborate 、 三乙胺 作用下， 以 N,N-二甲基甲酰胺 、 异丙醇 为溶剂， 反应 5.0h， 以41%的产率得到6-amino-6'-azido-6,6'-dideoxy-α,α'-trehalose
  参考文献：
  名称：

  Synthesis, Structure, and Inclusion Capabilities of Trehalose-Based Cyclodextrin Analogues (Cyclotrehalans)

  摘要：

  Concise and efficient strategies toward the synthesis of D-2h- and D-3h-symmetric cyclodextrin analogues alternating alpha,alpha'-trehalose disaccharide subunits and pseudoamide segments (cyclotrehalans, CTs) are reported. The conformational properties of these cyclooligosaccharides are governed by the rigidity of the alpha,alpha'-trehalose disaccharide repeating unit and the partial double-bond character of the N-(C=X) linkages. In contrast to the typical concave-shaped cavity of cyclodextrins (CDs), CTs feature a convex-shaped hydrophobic cavity in which the beta-face of the monosaccharide subunits is oriented toward the inner side, as supported by NMR and modeling (molecular mechanics and dynamics) studies. In the case of cyclodimeric CTs (CT2s), the existence of intramolecular hydrogen bonds results in collapsed cavities, too small to allow the formation of inclusion complexes with organic molecules. Cyclotrimeric CTs (CT3s) display cavity sizes that are intermediate between those of alpha CD and beta CD, ideally suited for the complexation of complementary guests with ternary symmetry such as adamantane 1-carboxylate (AC). The higher flexibility of the pseudoamide bridges as compared with classical glycosidic linkages endow these glyconanocavities with some conformational adaptability properties, making them better suited than CDs for complexation of angular guests, as seen from comparative inclusion capability experiments against the fluorescent probes 6-p-toluidinonaphthalene-2-sulfonate (TNS; linear) and 8-anilinonaphthalene-1-sulfonate (ANS; angular).

  DOI：

  10.1021/jo800048s
• 作为产物：
  描述：

  海藻糖 在 偶氮二甲酸二异丙酯 、 三苯基膦 、 迭氮酸 作用下， 以 1,4-二氧六环 、 甲苯 为溶剂， 反应 66.5h， 以11%的产率得到6,6'-diazido-6,6'-dideoxy-α,α-trehalose
  参考文献：
  名称：

  流动化学动力学研究揭示了容易获得不对称海藻糖类似物的反应条件†

  摘要：

  在微反应器中对海藻糖（一种广泛发现的对称植物二糖）的单功能化进行了研究，以提供有价值的动力学见解，从而提高去对称化产率，并开发用于大规模单功能化的反应序列，从而可以探查海藻糖的生物学功能。

  DOI：

  10.1039/c0ob00226g

文献信息

• Red Emitting Neutral Fluorescent Glycoconjugates for Membrane Optical Imaging
  作者：Sébastien Redon、Julien Massin、Sandrine Pouvreau、Evelien De Meulenaere、Koen Clays、Yves Queneau、Chantal Andraud、Agnès Girard-Egrot、Yann Bretonnière、Stéphane Chambert

  DOI：10.1021/bc500047r

  日期：2014.4.16

  A family of neutral fluorescent probes was developed, mimicking the overall structure of natural glycolipids in order to optimize their membrane affinity. Nonreducing commercially available di- or trisaccharidic structures were connected to a push–pull chromophore based on dicyanoisophorone electron-accepting group, which proved to fluoresce in the red region with a very large Stokes shift. This straightforward

  开发了一个中性荧光探针家族，模仿天然糖脂的整体结构，以优化其膜亲和力。非还原性市售的二糖或三糖结构与基于双氰基异佛尔酮电子接受基团的推挽发色团相连，事实证明该发色团在红色区域发出了很大的斯托克斯位移。这种简单明了的合成策略为一系列探针带来了结构变异，并对其光学，生物物理和生物学特性进行了研究。使用Langmuir单层平衡技术，在模型系统上评估了不同探针在膜中的插入特性。对肌肉细胞进行的共聚焦荧光显微镜检查显示完全不同的定位和加载效率，具体取决于探针的结构。与市售的ANEPPS（一种常用的膜成像染料家族）相比，最有效的探针显示出相似的亮度，但观察到更清晰的图案。根据这项研究，带有一个发色团，有限的碳水化合物部分大小和整体杆状形状的化合物可获得最佳结果。
• [EN] BRARTEMICIN ANALOGUES<br/>[FR] ANALOGUES DE BRARTÉMICINE
  申请人：VICTORIA LINK LTD

  公开号：WO2019088854A1

  公开（公告）日：2019-05-09

  The invention relates to brartemicin analogues of Formula (IV) and their uses. These compounds are potent Mincle agonists and Th1-stimulating vaccine adjuvants.

  这项发明涉及公式（IV）的brartemicin类似物及其用途。这些化合物是强效的Mincle激动剂和Th1刺激疫苗佐剂。
• Direct azidation of unprotected carbohydrates under Mitsunobu conditions using hydrazoic acid
  作者：Céline Besset、Stéphane Chambert、Bernard Fenet、Yves Queneau

  DOI：10.1016/j.tetlet.2009.09.173

  日期：2009.12

  A single step procedure for the direct and regioselective synthesis of carbohydrate azides from unprotected sugars using hydrazoic acid under Mitsunobu conditions is reported. A series of mono-, di-, or triazido polyhydroxylated systems are described.

  报道了在Mitsunobu条件下使用酸从未保护的糖直接和区域选择性合成碳水化合物叠氮化物的一步步骤。描述了一系列的单，双或三叠氮基多羟基化体系。
• 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。
• Supramolecular structures of substituted α,α′-trehalose derivatives
  作者：Thomas C. Baddeley、Iain G. Davidson、Christopher Glidewell、John N. Low、Janet M. S. Skakle、James L. Wardell

  DOI：10.1107/s0108768104010912

  日期：2004.8.1

  The structures of five substituted α,α′-trehalose trehalose derivatives have been determined, and these are compared with those of four previously published analogues. In 2,2′,3,3′,4,4′-hexaacetato-6,6′-bis-O-methylsulfonyl-α,α′-trehalose, C₂₆H₃₈O₂₁S₂, where the molecules lie across twofold rotation axes in the space group C2, a single C—H...O=S hydrogen bond links the molecules into sheets. 2,2′,3,3′,4,4′-Hexaacetato-6,6′-bis-O-(4-toluenesulfonyl)-α,α′-trehalose, C₃₈H₄₆O₂₁S₂, crystallizes with Z′ = 2 in the space group P2₁2₁2₁ and a combination of three C—H...O hydrogen bonds, each having a carbonyl O atom as an acceptor, and a C—H...π(arene) hydrogen bond link the molecules into a three-dimensional framework. 2,2′,3,3′,4,4′-Hexaacetato-6,6′-diazido-α,α′-trehalose, C₂₄H₃₂N₆O₁₅, crystallizes as a partial ethanol solvate and three C—H...O hydrogen bonds link the substituted trehalose molecules into a three-dimensional framework. In 2,2′,3,3′-tetraacetato-6,6′-bis(N-acetylamino)-α,α′-trehalose dihydrate, C₂₄H₃₆N₂O₁₅·2H₂O, the substituted trehalose molecules lie across twofold rotation axes in the space group P2₁2₁2 and a three-dimensional framework is generated by the combination of O—H...O and N—H...O hydrogen bonds. The diaminotrehalose molecules in 6,6′-diamino-α,α′-trehalose dihydrate, C₁₂H₂₄N₂O₉.2(H₂O), lie across twofold rotation axes in the space group P4₃2₁2: a single O—H...N hydrogen bond links the trehalose molecules into sheets, which are linked into a three-dimensional framework by O—H...O hydrogen bonds.

  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。