ditert-butyl (1S,2S,4S,5R)-4,5-dihydroxycyclohexane-1,2-dicarboxylate | 221344-09-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ditert-butyl (1S,2S,4S,5R)-4,5-dihydroxycyclohexane-1,2-dicarboxylate
• CAS: 221344-09-8
• 化学式: C₁₆H₂₈O₆
• 分子量: 316.395
• InChiKey: BZYAKODIGWNGCA-FIQHERPVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  93.1
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ditert-butyl (1S,2S,4S,5R)-4,5-dihydroxycyclohexane-1,2-dicarboxylate 在 palladium on activated charcoal 三氟甲磺酸 、 氢气 、 二正丁基氧化锡 作用下， 以 甲醇 、 二氯甲烷 、 苯 为溶剂， 反应 35.0h， 生成
  参考文献：
  名称：

  Mimics of ganglioside GM1 as cholera toxin ligands: replacement of the GalNAc residueElectronic supplementary information (ESI) available: synthetic details, product characterisations and full NOE contact list. See http://www.rsc.org/suppdata/ob/b2/b210503a/

  摘要：

  描述了两种新的霍乱毒素（CT）配体（4和5）。这两种新配体是从已知的GM1类似物2和3开始设计的，通过将它们的GalNAc残基替换为C4异构体GlcNAc。根据分子建模预测，等价对2-4和3-5的构象特性非常相似，它们对CT的亲和力也在同一数量级。NMR实验也证实了5占据毒素的GM1结合位点，并揭示了其结合构象。

  DOI：

  10.1039/b210503a
• 作为产物：
  描述：

  Cyclohex-4-ene-1,2-dicarboxylic acid bis-((S)-1-ethoxycarbonyl-ethyl) ester 在 lithium hydroxide 、 osmium (III) chloride 、 十二/十四烷基二甲基氧化胺 作用下， 以 甲醇 、 水 、 丙酮 、 苯 为溶剂， 反应 24.0h， 生成 ditert-butyl (1S,2S,4S,5R)-4,5-dihydroxycyclohexane-1,2-dicarboxylate
  参考文献：
  名称：

  Synthesis of a Pseudo Tetrasaccharide Mimic of Ganglioside GM1

  摘要：

  The pseudo tetrasaccharide 2 was designed to mimic ganglioside GM1, the membrane receptor of both the cholera toxin and of the heat-labile toxin of E. coli. Compound 2 retains the Gal and Neu5Ac recognition determinant of GM1 and uses as the scaffold element a new, conformationally restricted cyclohexanediol (DCCHD 3), with the same relative and absolute configuration of natural galactose; The diol 3 was enantioselectively synthesized by an asymmetric Diels-Alder reaction, followed by dihydroxylation of the resulting cyclohexene. Glycosylation of 3 with the sialyl donor 17 and the Gal beta(l-3)GalNAc donor 15, followed by removal of the protecting groups, completed the synthesis of 2.

  DOI：

  10.1002/(sici)1099-0690(199906)1999:6<1311::aid-ejoc1311>3.0.co;2-w

文献信息

• Intramolecular Carbohydrate-Aromatic Interactions and Intermolecular van der Waals Interactions Enhance the Molecular Recognition Ability of GM1 Glycomimetics for Cholera Toxin
  作者：Anna Bernardi、Daniela Arosio、Donatella Potenza、Inmaculada Sánchez-Medina、Silvia Mari、F. Javier Cañada、Jesús Jiménez-Barbero

  DOI：10.1002/chem.200400084

  日期：2004.9.20

  has allowed their interactions with the toxin to be explained at the atomic level. It is shown that intramolecular van der Waals and CH-pi carbohydrate-aromatic interactions define the conformational properties of 7, which adopts a three-dimensional structure significantly preorganized for proper interaction with the toxin. The exploitation of this kind of sugar-aromatic interaction, which is very well

  描述了两种GM1糖模拟物6和7的设计和合成，以及在游离状态下以及与霍乱毒素复合后对其构象的分析。这些分别包含（R）-环己基乳酸和（R）-苯基乳酸片段的化合物显示出对霍乱毒素的显着亲和力。在分子模型技术的辅助下，对毒素/拟糖复合物进行的详细NMR光谱研究已在原子水平上解释了它们与毒素的相互作用。结果表明，分子内范德华力和CH-pi碳水化合物-芳香族相互作用定义了7的构象特性，该构型采用明显预组织的与毒素正确相互作用的三维结构。利用这种糖-芳香相互作用，
• A Simple Model System for the Study of Carbohydrate−Aromatic Interactions
  作者：Giancarlo Terraneo、Donatella Potenza、Angeles Canales、Jesus Jiménez-Barbero、Kim K. Baldridge、Anna Bernardi

  DOI：10.1021/ja066633g

  日期：2007.3.1

  establishment of intramolecular interactions between a monosaccharide and a nearby phenyl ring. A group of molecules containing four different monosaccharides (glucose, galactose, N-acetyl-glucosamine, and N-acetyl-galactosamine) was synthesized and used to investigate the extent and nature of this carbohydrate-arene interaction, as well as the effect on the overall 3D structure of the molecules involved. The sugar-aromatic

  确定了一种分子支架，它能够在单糖和附近的苯环之间建立分子内相互作用。合成了一组含有四种不同单糖（葡萄糖、半乳糖、N-乙酰-氨基葡萄糖和 N-乙酰-半乳糖）的分子，并用于研究这种碳水化合物-芳烃相互作用的程度和性质，以及对所涉及分子的整体 3D 结构。糖-芳香族距离通过分子模型支持的严格 NMR 研究进行评估，发现在整个系列中是恒定的，与糖的性质和连接两个元素的片段的构象行为无关。B3LYP/DZV(2d,p) 理论水平的从头算计算能够分析相互作用的电子性质。该研究表明，如果有机会，可以建立持久的分子内芳香-糖相互作用，并且可以显着影响整体分子形状和能量。这些结果对寡糖结构模拟物的设计具有重要意义。
• Sugar Mimics:  An Artificial Receptor for Cholera Toxin
  作者：Anna Bernardi、Anna Checchia、Paola Brocca、Sandro Sonnino、Fabio Zuccotto

  DOI：10.1021/ja983567c

  日期：1999.3.1

  paper describes the pseudosugar 2 [Galβ1−3GalNAcβ1−4(NeuAcα2−3)DCCHD], a high affinity binder of cholera toxin (CT). The molecule was designed using molecular modeling techniques to mimic the natural CT membrane receptor, ganglioside GM1. The central residue of GM1, a 3,4-disubstituted galactose unit, was recognized as the ganglioside scaffold element and substituted with a conformationally locked cyclohexanediol

  该论文描述了伪糖 2 [Galβ1−3GalNAcβ1−4(NeuAcα2−3)DCCHD]，一种霍乱毒素 (CT) 的高亲和力结合剂。该分子是使用分子建模技术设计的，以模拟天然 CT 膜受体神经节苷脂 GM1。GM1 的中心残基是一个 3,4-二取代的半乳糖单元，被认为是神经节苷脂支架元件，并被构象锁定的环己二醇 (DCCHD) 取代。DCCHD 使用对映选择性 Diels Alder 方法和在赤道位置的区域选择性 α-唾液酸化以对映纯形式合成。用Galβ(1-3)GalNAc供体进行糖基化完成了2的合成。发现2的溶液结构及其与CT的结合能力类似于GM1寡糖的那些。
• Second generation mimics of ganglioside GM1 as artificial receptors for cholera toxin: replacement of the sialic acid moiety
  作者：Anna Bernardi、Laura Carrettoni、Antonio Grosso Ciponte、Diego Monti、Sandro Sonnino

  DOI：10.1016/s0960-894x(00)00428-5

  日期：2000.10

  In a program directed towards the design and synthesis of mimics of ganglioside GM1, the NeuAc recognition domain was replaced by simple hydroxy acids, and the affinity of the new ligands to the cholera toxin was determined by fluorescence spectroscopy. The (R)-lactic acid derivative 4 was found to display the highest affinity of the series (KD = 190 microM).

  在针对神经节苷脂GM1模拟物的设计和合成的程序中，NeuAc识别域被简单的羟基酸取代，新配体对霍乱毒素的亲和力通过荧光光谱法确定。发现（R）-乳酸衍生物4显示出该系列的最高亲和力（KD = 190 microM）。
• Stereoselective Synthesis of Conformationally Constrained Cyclohexanediols:  A Set of Molecular Scaffolds for the Synthesis of Glycomimetics
  作者：Anna Bernardi、Daniela Arosio、Leonardo Manzoni、Fabrizio Micheli、Alessandra Pasquarello、Pierfausto Seneci

  DOI：10.1021/jo015570b

  日期：2001.9.1

  The practical, stereoselective synthesis of the three diastereoisomeric 1,2-trans-dicarboxy-4,5-cyclohexanediols. 1-3 (DCCHDs) is described, starting from a common precursor, easily available in both enantiomeric forms. The regioselective derivatization of all functional groups of I is also reported. The three DCCHDs are locked in a single chair conformation and thus can be used to mimic vicinally disubstituted monosaccharides of any relative configuration.