tert-butyl N-[31-[(2-methylpropan-2-yl)oxycarbonylamino]-2,5,8,11,18,21,24,27-octaoxatricyclo[26.4.0.012,17]dotriaconta-1(28),12(17),13,15,29,31-hexaen-14-yl]carbamate | 514204-35-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: tert-butyl N-[31-[(2-methylpropan-2-yl)oxycarbonylamino]-2,5,8,11,18,21,24,27-octaoxatricyclo[26.4.0.012,17]dotriaconta-1(28),12(17),13,15,29,31-hexaen-14-yl]carbamate
• CAS: 514204-35-4
• 化学式: C₃₄H₅₀N₂O₁₂
• 分子量: 678.777
• InChiKey: UYSNOKXPWRWVCN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  48
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  151
• 氢给体数：
  2
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  N,N'-二环己基碳二亚胺 、 N-3,5-di-tert-butylbenzyl-5-amino-valeric acid 、 tert-butyl N-[31-[(2-methylpropan-2-yl)oxycarbonylamino]-2,5,8,11,18,21,24,27-octaoxatricyclo[26.4.0.012,17]dotriaconta-1(28),12(17),13,15,29,31-hexaen-14-yl]carbamate 以 氯仿 为溶剂， 反应 1.5h， 生成
  参考文献：
  名称：

  测定宿主[3]轮烷的结合和细胞内转运能力

  摘要：

  在主体[2]轮烷（HR）的存在下，可以增强化合物的细胞渗透性。HR的有效浓度受到HR和所输送化合物的复合物形成的化学计量的限制。我们推测在膜通过过程中，HR和客人之间会形成复杂的形式。为了进一步探讨来宾绑定和来宾传递之间的关系并获得更有效的传递设备，我们在本报告中介绍了环烷-[3]轮烷（Cy3R）的第一个示例，该环烷具有两个轮子和一个环烷作为阻止组。将Cy3R的特性与新的环烷-[2]轮烷（Cy2R）进行了比较，后者具有与Cy3R相同的环烷兜，但只有一个轮子。Cy3R的第二个轮子可以形成其他非共价键，例如盐桥，阳离子-π相互作用或芳族-芳族相互作用，以及适当官能化的客人。我们通过流式细胞仪分析显示，Cy3R将Fl-AVWAL（76％）和较小程度的Fl-QEAVD（26％）转移到活细胞中。细胞内F1肽的水平与浓度有关，并且在很大程度上不受温度和ATP的影响，这表明Cy3R·F1肽复合物可通过细

  DOI：

  10.1021/jo0623641
• 作为产物：
  描述：

  二碳酸二叔丁酯 、 4',5''-dinitro-DB24C8 在 palladium on activated charcoal 氢气 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 2.0h， 以90%的产率得到tert-butyl N-[31-[(2-methylpropan-2-yl)oxycarbonylamino]-2,5,8,11,18,21,24,27-octaoxatricyclo[26.4.0.012,17]dotriaconta-1(28),12(17),13,15,29,31-hexaen-14-yl]carbamate
  参考文献：
  名称：

  Structure−Function Relationship of Amino Acid−[2]Rotaxanes

  摘要：

  Synthetic methodology was developed to construct amino acid-[2]rotaxanes that have phenylalanine and 3,5-di-tert-butylbenzene as blocking groups and dibenzo-24-crown-8, derivatized with either N-acetylargininyl or a carboxylic group, as the ring. A relative measure of the intramolecular interaction energies between the functional groups in DMSO/water mixtures is obtained by comparing their pK(a) values. Rotaxane structures were investigated through 2D NMR analysis and molecular dynamics simulations. Association constants for complexes of amino acids and rotaxanes in various protonation states were determined in a variety of solvent systems by H-1 NMR analysis. The unique intracomponent interactions that exist in the rotaxanes and their ability to act as artificial receptors are discussed.

  DOI：

  10.1021/jo026530q

文献信息

• Host−[2]Rotaxane:  Advantage of Converging Functional Groups for Guest Recognition
  作者：Inese Smukste、Brian E. House、David B. Smithrud

  DOI：10.1021/jo026522+

  日期：2003.4.1

  A host-[2]rotaxane was constructed by converting a diaminophenylcalix[4]arene into a [2]rotaxane using the DCC-rotaxane method (Zehnder, D.; Smithrud, D. B. Org. Lett. 2001, 16, 2485-2486). N-Ac-Arg groups were attached to the dibenzo-24-crown-8 ring of the rotaxane to provide a convergent functional group. To demonstrate the advantage provided by the rotaxane architecture for recognition of guests that contain a variety of functional groups, association constants (K-A) for N-Ac-Trp, indole, N-Ac-Gly, fluorescein, 1-(dimethylamino)-5-naphthalenesulfonate, and pyrene bound to the [2]rotaxane were determined by performing H-1 NMR and fluorescence spectroscopic experiments. The host-[2]rotaxane had the highest affinity for fluorescein with a K-A = 4.6 x 106 M-1 in a 98/2 buffer (1 mM phosphate, pH 7)/DMSO solution. A comparison of K-A values demonstrates that both the aromatic pocket and ring of the host-[2]rotaxane contribute binding free energy for complexation. Association constants were also derived for the same guests bound to the diaminophenylcalix[4]arene and to a diphenylcalix[4]arene that contained arginine residues displayed in a nonconvergent fashion. The host-[2]rotaxane provides higher affinity and specificity for most guests than the host with divergent N-Ac-Arg groups of the one that only has an aromatic pocket. For example, the K-A for the complex of the host-[2]rotaxane and fluorescein in the DMSO/water mixture is more than 2 orders of magnitude greater than association constants derived for the other hosts.