7,37,44-Trimethoxy-9,12,32,35,45,48-hexaoxa-18,21,24,26-tetraza-25-phosphaundecacyclo[22.20.9.38,39.213,16.221,26.228,31.249,52.136,40.03,42.018,25.05,58]pentahexaconta-1(44),2,5,7,13,15,28(61),29,31(60),36,38,40(56),42,49(55),50,52(54),58,64-octadecaene | 1267779-21-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 7,37,44-Trimethoxy-9,12,32,35,45,48-hexaoxa-18,21,24,26-tetraza-25-phosphaundecacyclo[22.20.9.38,39.213,16.221,26.228,31.249,52.136,40.03,42.018,25.05,58]pentahexaconta-1(44),2,5,7,13,15,28(61),29,31(60),36,38,40(56),42,49(55),50,52(54),58,64-octadecaene
• 英文别名: 7,37,44-trimethoxy-9,12,32,35,45,48-hexaoxa-18,21,24,26-tetraza-25-phosphaundecacyclo[22.20.9.38,39.213,16.221,26.228,31.249,52.136,40.03,42.018,25.05,58]pentahexaconta-1(44),2,5,7,13,15,28(61),29,31(60),36,38,40(56),42,49(55),50,52(54),58,64-octadecaene
• CAS: 1267779-21-4
• 化学式: C₅₇H₆₃N₄O₉P
• 分子量: 979.122
• InChiKey: FEIKPZVYMWNYBO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.5
• 重原子数：
  71
• 可旋转键数：
  3
• 环数：
  22.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  96
• 氢给体数：
  0
• 氢受体数：
  13

反应信息

• 作为反应物：
  描述：

  7,37,44-Trimethoxy-9,12,32,35,45,48-hexaoxa-18,21,24,26-tetraza-25-phosphaundecacyclo[22.20.9.38,39.213,16.221,26.228,31.249,52.136,40.03,42.018,25.05,58]pentahexaconta-1(44),2,5,7,13,15,28(61),29,31(60),36,38,40(56),42,49(55),50,52(54),58,64-octadecaene 在 2,8,9-三甲基-2,5,8,9-四氮杂-1-磷双环(3,3,3)十一烷 作用下， 以 乙腈 为溶剂， 生成
  参考文献：
  名称：

  Superbases in Confined Space: Control of the Basicity and Reactivity of the Proton Transfer

  摘要：

  Endohedral functionalization of the molecular cavity of host molecules is in high demand in many areas of supramolecular chemistry. When highly reactive species are incarcerated in the confined space of a molecular cavity, deep changes of their chemical properties are expected. Here, we show that the superbasic properties of proazaphosphatranes can be improved in the confined space of the molecular cavity of hemicryptophane hosts. A general and modular procedure is described to prepare supramolecular superbases with various cavity sizes. The rate of proton transfer is strongly dependent on the shape and size of the inner cavity of the designed superbasic structure. Kinetic and thermodynamic data are strongly correlated to the space available around the basic center as revealed by the X-ray molecular structures analyses.

  DOI：

  10.1021/ja409444s
• 作为产物：
  描述：

  在 potassium tert-butylate 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 2.5h， 以80%的产率得到7,37,44-Trimethoxy-9,12,32,35,45,48-hexaoxa-18,21,24,26-tetraza-25-phosphaundecacyclo[22.20.9.38,39.213,16.221,26.228,31.249,52.136,40.03,42.018,25.05,58]pentahexaconta-1(44),2,5,7,13,15,28(61),29,31(60),36,38,40(56),42,49(55),50,52(54),58,64-octadecaene
  参考文献：
  名称：

  Encaging the Verkade’s Superbases: Thermodynamic and Kinetic Consequences

  摘要：

  Proazaphosphatranes, also known as Verkade's superbases, are nonionic species, which exhibit catalytic properties for a wide range of reactions. The properly designed host molecule 3 and its protonated counterpart [3 center dot H]Cl-+(-) were synthesized to study how confinement can modify the stability and the reactivity of a Verkade's superbase. The results show that the encapsulation does not alter the strong basicity of the proazaphosphatrane, but dramatically decreases the rate of proton transfer.

  DOI：

  10.1021/ja1110333
• 作为试剂：
  描述：

  蒽酮 、 富马酸二甲酯 在 7,37,44-Trimethoxy-9,12,32,35,45,48-hexaoxa-18,21,24,26-tetraza-25-phosphaundecacyclo[22.20.9.38,39.213,16.221,26.228,31.249,52.136,40.03,42.018,25.05,58]pentahexaconta-1(44),2,5,7,13,15,28(61),29,31(60),36,38,40(56),42,49(55),50,52(54),58,64-octadecaene 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以100%的产率得到
  参考文献：
  名称：

  Catalytic Activity of an Encaged Verkade’s Superbase in a Base-Catalyzed Diels–Alder Reaction

  摘要：

  Organocatalysis in a confined space has been performed through encapsulation of a proazaphosphatrane superbase in a hemicryptophane host. The resulting catalyst displays good to high catalytic activity in the base-catalyzed Diels-Alder reactions investigated. A comparison with the model superbase, which lacks a cavity, shows much higher diastereomeric excess with the encaged proazaphosphatrane for the reaction of 3-hydroxy-2-pyrone with N-methylmaleimide. The use of an encaged superbase as organocatalyst is unprecedented and highlights how the confinement may impact the stereoselectivity.

  DOI：

  10.1021/jo501457d

文献信息

• Encaging the Verkade’s Superbases: Thermodynamic and Kinetic Consequences
  作者：Pascal Dimitrov Raytchev、Alexandre Martinez、Heinz Gornitzka、Jean-Pierre Dutasta

  DOI：10.1021/ja1110333

  日期：2011.2.23

  Proazaphosphatranes, also known as Verkade's superbases, are nonionic species, which exhibit catalytic properties for a wide range of reactions. The properly designed host molecule 3 and its protonated counterpart [3 center dot H]Cl-+(-) were synthesized to study how confinement can modify the stability and the reactivity of a Verkade's superbase. The results show that the encapsulation does not alter the strong basicity of the proazaphosphatrane, but dramatically decreases the rate of proton transfer.
• Superbases in Confined Space: Control of the Basicity and Reactivity of the Proton Transfer
  作者：Bastien Chatelet、Heinz Gornitzka、Véronique Dufaud、Erwann Jeanneau、Jean-Pierre Dutasta、Alexandre Martinez

  DOI：10.1021/ja409444s

  日期：2013.12.11

  Endohedral functionalization of the molecular cavity of host molecules is in high demand in many areas of supramolecular chemistry. When highly reactive species are incarcerated in the confined space of a molecular cavity, deep changes of their chemical properties are expected. Here, we show that the superbasic properties of proazaphosphatranes can be improved in the confined space of the molecular cavity of hemicryptophane hosts. A general and modular procedure is described to prepare supramolecular superbases with various cavity sizes. The rate of proton transfer is strongly dependent on the shape and size of the inner cavity of the designed superbasic structure. Kinetic and thermodynamic data are strongly correlated to the space available around the basic center as revealed by the X-ray molecular structures analyses.