tetraethyl (4R,5S,31R,32S)-9,27-dimethoxy-12,24-dinitro-16,20,33,34-tetraoxo-1,3,6,15,17,19,21,30-octazanonacyclo[28.2.1.13,6.04,17.05,15.08,13.019,32.021,31.023,28]tetratriaconta-8,10,12,23,25,27-hexaene-4,5,31,32-tetracarboxylate | 444929-87-7

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: tetraethyl (4R,5S,31R,32S)-9,27-dimethoxy-12,24-dinitro-16,20,33,34-tetraoxo-1,3,6,15,17,19,21,30-octazanonacyclo[28.2.1.13,6.04,17.05,15.08,13.019,32.021,31.023,28]tetratriaconta-8,10,12,23,25,27-hexaene-4,5,31,32-tetracarboxylate
• CAS: 444929-87-7
• 化学式: C₄₀H₄₂N₁₀O₁₈
• 分子量: 950.83
• InChiKey: WSDRTGVQGUJVSL-AJXFNKDUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  68
• 可旋转键数：
  14
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  310
• 氢给体数：
  0
• 氢受体数：
  18

反应信息

• 作为反应物：
  描述：

  tetraethyl (4R,5S,31R,32S)-9,27-dimethoxy-12,24-dinitro-16,20,33,34-tetraoxo-1,3,6,15,17,19,21,30-octazanonacyclo[28.2.1.13,6.04,17.05,15.08,13.019,32.021,31.023,28]tetratriaconta-8,10,12,23,25,27-hexaene-4,5,31,32-tetracarboxylate 在 palladium 10% on activated carbon 、 氢气 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 20.0 ℃ 、137.9 kPa 条件下， 反应 6.0h， 生成
  参考文献：
  名称：

  Reassembly self-sorting triggered by heterodimerization

  摘要：

  我们在此报告一个由五个组分自排序系统组成，该系统包含形成异二聚体1·4和8·11，以及同二聚体14·14的分子夹具，溶剂为C6D5CD3/CDCl3。由组分1·1、8·8和14·14组成的三组分自排序混合物在加入4·4和11·11后发生触发重组自排序。

  DOI：

  10.1039/c1cc13288a
• 作为产物：
  描述：

  在 对甲苯磺酸 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 192.0h， 生成 tetraethyl (4R,5S,31R,32S)-9,27-dimethoxy-12,24-dinitro-16,20,33,34-tetraoxo-1,3,6,15,17,19,21,30-octazanonacyclo[28.2.1.13,6.04,17.05,15.08,13.019,32.021,31.023,28]tetratriaconta-8,10,12,23,25,27-hexaene-4,5,31,32-tetracarboxylate
  参考文献：
  名称：

  甘脲二聚体的非对映选择性形成：葫芦[n]脲合成的异构化机制和意义

  摘要：

  Cucurbit[6]uril (CB[6]) 是一种大环化合物，由甘脲和甲醛在一锅中制备，其分子识别特性使其成为深入研究的对象。CB[n] 形成机制的研究可能为 CB[n] 同系物和衍生物的定制合成提供见解，但由于 CB[n] 的复杂结构而受到阻碍。通过降低形成 S 形 (12S-18S) 和 C 形 (12C-18C) 亚甲基桥联甘脲二聚体的反应复杂性，我们已经能够探索 CB[n] 机制的基本步骤合成到以前不可能达到的水平。例如，我们提出了强有力的证据，证明 CB[n] 合成的机制是通过 S 形和 C 形二聚体的中介进行的。S 形和 C 形二聚体的相对自由能的第一次实验测定表明 C 形非对映异构体的热力学偏好 (1.55-3.25 kcal mol(-)(1))。这种热力学偏好不是因为自缔合、溶剂化或模板效应。此外，标记实验使我们能够阐明 S 形和 C 形非对映异构体之间这种酸催化平衡

  DOI：

  10.1021/ja025876f

文献信息

• Methylene-Bridged Glycoluril Dimers:  Synthetic Methods
  作者：Anxin Wu、Arindam Chakraborty、Dariusz Witt、Jason Lagona、Fehmi Damkaci、Marie A. Ofori、Jessica K. Chiles、James C. Fettinger、Lyle Isaacs

  DOI：10.1021/jo0258958

  日期：2002.8.1

  Cyclic ethers 5a,d-f and 25-26 undergo highly diastereoselective dimerization reactions to yield methylene-bridged glycoluril dimers with the formal extrusion of formaldehyde. Last, it is possible to perform selective heterodimerization reactions using both cyclic ethers and glycoluril derivatives bearing ureidyl NH groups. These reactions deliver the desired C- and S-shaped heterodimers with low to moderate

  亚甲基桥甘脲二聚体是葫芦素（CB [6]），其同系物（CB [n]）及其衍生物的基本组成部分。本文介绍了三种互补的合成C型和S型亚甲基桥甘脲二聚体的方法（29-34和37-44）。为此，我们制备了在其凸面上具有多种功能的甘脲衍生物（1a-d）。这些甘脲衍生物在碱性条件下（DMSO，t-BuOK）用1,2-双（卤甲基）芳烃6-15烷基化，得到4a-d和16-24，其中含有一个芳族邻二甲苯基环并可能具有亲核性脲基NH基团。带有潜在亲电环醚基团（5a-f）和25-28的甘脲衍生物是通过各种方法制备的，包括在回流的含多聚甲醛的TFA中进行缩合反应。在大多数情况下，在无水酸性条件下（PTSA，ClCH（2）CH（2）Cl，回流），4a-d和16-24与低聚甲醛的缩合反应可得到C形和S形亚甲基桥接的甘脲高产到高产。在许多情况下，优选以高非对映选择性形成C形化合物。环醚5a，df和25-26经历高度非对
• Synthesis, Crystal Structure of the Receptor Derived from Diethoxycarbonyl Glycoluril for Aromatic Amide Guest
  作者：Baohan Zhou、Baoming Xu、Li Ma、Meixi Wang、Kun Chen、Yanguo Chen

  DOI：10.1002/cjoc.201400477

  日期：2014.11

  The receptor derived from the diethoxycarbonyl glycoluril was synthesized and characterized by IR, 1H NMR, MS techniques and X‐ray single crystal analysis. Single crystal X‐ray diffraction reveals that the receptor remains monomeric because of its bulky t‐Bu groups on the side walls. Its unique binding properties for aromatic amides were studied through 1H NMR and IR techniques.

  合成了二乙氧基羰基甘脲的受体，并通过IR，1 H NMR，MS技术和X射线单晶分析对其进行了表征。单晶X射线衍射表明，由于其侧壁上的t- Bu基团庞大，因此该受体保持单体状态。通过1 H NMR和IR技术研究了其对芳族酰胺的独特结合性能。
• Self-Sorting:  The Exception or the Rule?
  作者：Anxin Wu、Lyle Isaacs

  DOI：10.1021/ja028913b

  日期：2003.4.1

  whether it is likely to become a more general phenomenon governing molecular recognition and self-assembly. To address this question we prepared a mixture comprising two of Davis' self-assembled ionophores, Rebek's tennis ball and calixarene tetraurea capsule, Meijer's ureidopyrimidinone, Reinhoudt's calixarene bis(rosette), and two molecular clips in CDCl(3) solution and observed the behavior of this

  在本文中，我们提出了一个问题，即设计系统中的自分类是否是异常行为，或者它是否可能成为控制分子识别和自组装的更普遍现象。为了解决这个问题，我们制备了一种混合物，包括两个戴维斯的自组装离子载体、Rebek 的网球和杯芳烃四脲胶囊、Meijer 的脲基嘧啶酮、Reinhoudt 的杯芳烃双（玫瑰花结）和 CDCl(3) 溶液中的两个分子夹，并观察了行为通过 (1)H NMR 对这个集合进行了分析。正如假设的那样，观察到了高保真自分类行为。描述了几个关键变量——温度、浓度、平衡常数和竞争者的存在——对自分类保真度的影响。这些结果表明，自排序既不是例外也不是规则。
• Molecular Clips Form Isostructural Dimeric Aggregates from Benzene to Water
  作者：Anxin Wu、Pritam Mukhopadhyay、Arindam Chakraborty、James C. Fettinger、Lyle Isaacs

  DOI：10.1021/ja0486972

  日期：2004.8.1

  We report the synthesis and characterization of eight C-shaped methylene-bridged glycoluril dimers (1-8) bearing hydrogen-bonding amide groups on their aromatic rings. Compounds 1-6 undergo tight dimerization in CDCl3 solution (K-s > 9 x 10(5) M-1); binary mixtures of 1-7 form mixtures of homodimers and heterodimers in moderately selective dimerization processes (0.23 less than or equal to K-eq less than or equal to 768; 0.253 less than or equal to chi(AB) < 0.933). The high affinity formation of 1(.)1-6(.)6 is due to the commensurate nature of the geometrical constraints imposed by the pi-pi interactions and only two hydrogen bonds. The differential response of the strengths of the pi-pi interactions and H-bonds of 2(.)2 to changes in solvent polarity-from C6D6 to D2O-results in the formation of a solvent-independent isostructural aggregate that exhibits high affinity dimerization across the full range of solvents.
• Self-Sorting Molecular Clips
  作者：Soumyadip Ghosh、Anxin Wu、James C. Fettinger、Peter Y. Zavalij、Lyle Isaacs

  DOI：10.1021/jo8009424

  日期：2008.8.1

  We report the synthesis and characterization of 12 C-shaped methylene-bridged glycoluril dimers (1-12) bearing H-bonding groups on their aromatic rings. Compounds 1, 2, (+/-)-4a, (+/-)-5, (+/-)-7, and 8 form tightly associated homodimers in CDCl3, due to the combined driving force of pi-pi and H-bonding interactions. Compounds 2, ()-5, and 8, having disparate spatial distribution of their H-bonding groups, display the ability to efficiently distinguish between self and nonself even within three-component mixtures in CDCl3. When the spatial distributions of the H-bonding groups of the molecular clips are similar (e.g., 1 and 2), a mixture of homodimers and heterodimers is formed. The effect of various structural modifications (e.g., chirality, side chain steric bulk, number and pattern of H-bonds) on the strength of self-assembly and the fidelity of self-sorting are presented. On the basis of these results we prepared self-sorting systems comprising three (e.g., 1, (+/-)-5, and (+/-)-7) and even four (2, (+/-)-5, 9, and 10) components. The potential of molecular clips 1-12 as robust, functionalizable, self-sorting modules to control the noncovalent interaction network in systems chemistry studies is described.