5,11,17,23-tetrakis-(3-azidomethyl)-25,26,27,28-tetrapropoxy-calix[4]arene | 949894-55-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 5,11,17,23-tetrakis-(3-azidomethyl)-25,26,27,28-tetrapropoxy-calix[4]arene
• 英文别名: 5,11,17,23-Tetrakis(azidomethyl)-25,26,27,28-tetrapropoxypentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3,5,7(28),9,11,13(27),15(26),16,18,21(25),22-dodecaene
• CAS: 949894-55-7
• 化学式: C₄₄H₅₂N₁₂O₄
• 分子量: 812.975
• InChiKey: DHPDHXHJTBCDBA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.6
• 重原子数：
  60
• 可旋转键数：
  20
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  94.4
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  5,11,17,23-tetrakis-(3-azidomethyl)-25,26,27,28-tetrapropoxy-calix[4]arene 、 N-Boc-氨基丙炔 在 copper(ll) sulfate pentahydrate 、 sodium ascorbate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 36.0h， 以0.17 g的产率得到
  参考文献：
  名称：

  A Stimulus-Responsive Shape-Persistent Micelle Bearing a Calix[4]arene Building Block: Reversible pH-Dependent Transition between Spherical and Cylindrical Forms

  摘要：

  A series of cationic calix[4]arene-based lipids with alkyl chains of varying length were newly synthesized, and the ones with propyl and hexyl tails, denoted by CaL[4]C3 and C6, respectively, were found to form spherical micelles at low pH (protonated state of the amine headgroup). Upon deprotonation with increasing pH, CaL[4]C3 showed a sphere-to-cylinder transition, while CaL[4]C6 changed from sphere, to cylinder, to monolayer vesicle. Synchrotron small-angle X-ray scattering (SAXS) patterns from both spherical and cylindrical CaL[4]C3 micelles exhibited a sharp intensity minimum, indicating shape monodispersity. The monodispersity of the CaL[4]C3 spherical micelles was further confirmed by analytical ultracentrifugation (AUC). SAXS, AUC, and static light scattering agreeingly indicated an aggregation number of 6. In contrast, CaL[4]C6 exhibited polydispersity with an average aggregation number of 12. When the number of carbons of the alkyl chain was increased to 9 (CaL[4]C9), cylinder formed at low pH, while at high pH, no clear morphology could be observed. The present results indicate that a very precise combination of tail length, head volume, and rigidity of the building block is required to produce shape-persistent micelles and that the shape-persistence can be maintained upon a structural transition. An attempt to reconstruct a molecular model for the spherical CaL[4]C3 micelle was made With an ab initio shape determining program.

  DOI：

  10.1021/la2037668
• 作为产物：
  描述：

  25,26,27,28-tetrapropyloxycalix[4]arene 在 盐酸 、 sodium azide 、 磷酸 、 溶剂黄146 作用下， 以 1,4-二氧六环 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 132.0h， 生成 5,11,17,23-tetrakis-(3-azidomethyl)-25,26,27,28-tetrapropoxy-calix[4]arene
  参考文献：
  名称：

  A Stimulus-Responsive Shape-Persistent Micelle Bearing a Calix[4]arene Building Block: Reversible pH-Dependent Transition between Spherical and Cylindrical Forms

  摘要：

  A series of cationic calix[4]arene-based lipids with alkyl chains of varying length were newly synthesized, and the ones with propyl and hexyl tails, denoted by CaL[4]C3 and C6, respectively, were found to form spherical micelles at low pH (protonated state of the amine headgroup). Upon deprotonation with increasing pH, CaL[4]C3 showed a sphere-to-cylinder transition, while CaL[4]C6 changed from sphere, to cylinder, to monolayer vesicle. Synchrotron small-angle X-ray scattering (SAXS) patterns from both spherical and cylindrical CaL[4]C3 micelles exhibited a sharp intensity minimum, indicating shape monodispersity. The monodispersity of the CaL[4]C3 spherical micelles was further confirmed by analytical ultracentrifugation (AUC). SAXS, AUC, and static light scattering agreeingly indicated an aggregation number of 6. In contrast, CaL[4]C6 exhibited polydispersity with an average aggregation number of 12. When the number of carbons of the alkyl chain was increased to 9 (CaL[4]C9), cylinder formed at low pH, while at high pH, no clear morphology could be observed. The present results indicate that a very precise combination of tail length, head volume, and rigidity of the building block is required to produce shape-persistent micelles and that the shape-persistence can be maintained upon a structural transition. An attempt to reconstruct a molecular model for the spherical CaL[4]C3 micelle was made With an ab initio shape determining program.

  DOI：

  10.1021/la2037668

文献信息

• Micelles consisting of choline phosphate-bearing Calix[4]arene lipids
  作者：Shota Fujii、Koichi Nishina、Shimpei Yamada、Shinichi Mochizuki、Noboru Ohta、Atsushi Takahara、Kazuo Sakurai

  DOI：10.1039/c4sm01355g

  日期：——

  Choline phosphate bearing calix[4]arene based lipids form monodispersed micelles, and the micelles are taken up by cells through CP–PC interactions.

  胆碱磷酸酯基卡利克斯[4]芳烃基脂质形成单分散胶束，这些胶束通过CP-PC相互作用被细胞吸收。
• Synthesis of sialoclusters appended to calix[4]arene platforms via multiple azide-alkyne cycloaddition. New inhibitors of hemagglutination and cytopathic effect mediated by BK and influenza A viruses
  作者：Alberto Marra、Lisa Moni、Daniele Pazzi、Alfredo Corallini、Deborah Bridi、Alessandro Dondoni

  DOI：10.1039/b800598b

  日期：——

  Tetra- and octavalent sialoside clusters were prepared in good yields exploiting for the first time the multiple copper-catalyzed cycloaddition of a propargyl thiosialoside with calix[4]arene polyazides. The cycloadducts featured the hydrolytically stable carbon-sulfur bond at the anomeric position and the 1,4-disubstituted triazole ring as the spacer between the sialic acid moieties and the platform. It was demonstrated that these unnatural motifs did not hamper the desired biological activity of the sialoclusters. In fact, they were able to inhibit, at submillimolar concentrations, the hemagglutination and the viral infectivity mediated both by BK and influenza A viruses.

  通过首次利用丙炔基硫代糖苷与钙[4]炔多氮化物的多重铜催化环加成反应，制备出了四价和八价的硫代糖苷簇，并获得了良好的收率。这些环加成物的特点是在同分异构位上具有水解稳定的碳硫键，而 1,4-二取代的三唑环则是硅杂羧酸分子与平台之间的间隔。研究表明，这些非天然结构并不妨碍硅脂环的预期生物活性。事实上，在亚摩尔浓度下，它们能够抑制 BK 病毒和甲型流感病毒介导的血凝和病毒传染性。
• Glutamic Acids Bearing Calix[4]arene Micelles: pH-Controllable Aggregation Number Corresponding to Regular Polyhedra
  作者：Shota Fujii、Rintaro Takahashi、Kazuo Sakurai

  DOI：10.1021/acs.langmuir.7b00603

  日期：2017.4.25

  the change in the lipid conformation corresponding to the pH conditions. Interestingly, at acidic and basic pH, the spherical micelles demonstrated monodispersity in terms of the aggregation number, which agreed with the vertex numbers of Platonic solids, indicating the formation of Platonic micelles. At acidic and basic pH, the lipid conformations were almost identical, but there was a slight difference

  我们制备了一种新的基于杯[4]芳烃的脂质，其含有谷氨酸作为亲水基团。谷氨酸部分的α-胺和γ-羧酸基团使头基的状态从阳离子到两性离子，然后随pH的增加而连续变化。伴随该头基改变，脂质的胶束经历了从球形到圆柱形再到球形的形态转变。形态转变归因于与pH条件相对应的脂质构象的变化。有趣的是，在酸性和碱性pH下，球形胶束在聚集数方面表现出单分散性，这与柏拉图固体的顶点数一致，表明柏拉图胶束的形成。在酸性和碱性pH下，脂质构型几乎相同，但亲水体积略有不同，这可能会影响脂质在胶束中的堆积行为，并解释聚集数的差异。这项研究清楚地证明了胶束的精确的pH可控的聚集数，该胶束属于柏拉图胶束系统。
• Upper Rim Appended Hybrid Calixarenes via Click Chemistry
  作者：Sean P. Bew、Rebecca A. Brimage、Nathalie L'Hermit、Sunil V. Sharma

  DOI：10.1021/ol071047t

  日期：2007.9.1

  We report the application of "click" chemistry for the synthesis of hybrid calixarenes appended on the upper rim with carbohydrate and N,C-protected alpha-amino acids. The chemoselective N- or C-deprotection of the (x-amino acids and their subsequent transformation into dipeptides is described. The first example of a chemo-enzymatic synthesis on upper rim derived calix[4]arenes using trans-sialidase affords sialylated lactose calix[4]arenes. Our innovative chemo-enzymatic process paves the way for further applications.
• Synthesis and glycosidase inhibition properties of triazole-linked calixarene–iminosugar clusters
  作者：Alberto Marra、Renaud Zelli、Giuseppe D'Orazio、Barbara La Ferla、Alessandro Dondoni

  DOI：10.1016/j.tet.2014.10.035

  日期：2014.12

  Calixarene iminosugar derivatives bearing four 1-deoxynojirimycin units at the upper or lower rim of calix[4]arenes in a fixed cone conformation were synthesized by copper-catalyzed azide-alkyne cyclo-addition (CuAAC) and their inhibitory activity was evaluated against five glycosidases. Modest but significant affinity enhancements of up to seven per 1-deoxynojirimycin unit over the monovalent iminosugar derivative were observed for the inhibition of Jack bean (Canavalia ensiformis) alpha-mannosidase. It was also demonstrated that the residual copper ions did not contribute to the inhibitory properties of the newly prepared calixarene-based multivalent iminosugars. (C) 2014 Elsevier Ltd. All rights reserved.