5,17-bis(N-tert-butoxycarbonylaminomethyl)-11,23-bis(ethoxycarbonyl)-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene | 1027504-15-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 5,17-bis(N-tert-butoxycarbonylaminomethyl)-11,23-bis(ethoxycarbonyl)-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene
• 英文别名: Diethyl 25,26,27,28-tetrakis(2-ethoxyethoxy)-11,23-bis[[(2-methylpropan-2-yl)oxycarbonylamino]methyl]pentacyclo[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-5,17-dicarboxylate
• CAS: 1027504-15-9
• 化学式: C₆₂H₈₆N₂O₁₆
• 分子量: 1115.37
• InChiKey: LGSLLJFFRJSNPG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.9
• 重原子数：
  80
• 可旋转键数：
  34
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  203
• 氢给体数：
  2
• 氢受体数：
  16

反应信息

• 作为反应物：
  描述：

  5,17-bis(N-tert-butoxycarbonylaminomethyl)-11,23-bis(ethoxycarbonyl)-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene 在 正丁基锂 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 18.0h， 生成 5,17-bis(aminomethyl)-11,23-bis(bis(1-methylimidazol-2-yl)hydroxymethyl)-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene
  参考文献：
  名称：

  Dinuclear Bisimidazolyl-Cu(II) Calix[4]arenes as Metalloenzyme Models. Synthesis and Bifunctional Catalysis in Phosphate Diester Transesterification

  摘要：

  Calix[4]arenes functionalized with two catalytic bisimidazolyl-Cu(II) centers and two additional hydroxymethyl (2-Cu-2) or aminomethyl groups (3-Cu-2) were synthesized as models for enzymes that cleave phosphate diester bonds. The kinetics of 2-Cu-2 and 3-Cu-2 in the catalysis of the intramolecular transesterification of the RNA model substrate 2-hydroxypropyl-p-nitrophenyl phosphate were compared with those of the parent calix[4]arene 1-Cu-2, lacking the two additional functional groups. Under neutral conditions, all complexes show high rate enhancements due to the cooperative action of the Cu(II) ions. The kinetics indicate for 3-Cu-2 bifunctional catalytic effects. At the pH optimum of 7.4 at least one amine is protonated, which can assist as a general acid in the binding and activation of the substrate.

  DOI：

  10.1021/jo9905266
• 作为产物：
  描述：

  11,23-bis(ethoxycarbonyl)-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene 在 palladium on activated charcoal 氯化亚砜 、 sodium azide 、 氢气 作用下， 以 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 三氟乙酸 为溶剂， 反应 114.0h， 生成 5,17-bis(N-tert-butoxycarbonylaminomethyl)-11,23-bis(ethoxycarbonyl)-25,26,27,28-tetrakis(2-ethoxyethoxy)calix[4]arene
  参考文献：
  名称：

  Dinuclear Bisimidazolyl-Cu(II) Calix[4]arenes as Metalloenzyme Models. Synthesis and Bifunctional Catalysis in Phosphate Diester Transesterification

  摘要：

  Calix[4]arenes functionalized with two catalytic bisimidazolyl-Cu(II) centers and two additional hydroxymethyl (2-Cu-2) or aminomethyl groups (3-Cu-2) were synthesized as models for enzymes that cleave phosphate diester bonds. The kinetics of 2-Cu-2 and 3-Cu-2 in the catalysis of the intramolecular transesterification of the RNA model substrate 2-hydroxypropyl-p-nitrophenyl phosphate were compared with those of the parent calix[4]arene 1-Cu-2, lacking the two additional functional groups. Under neutral conditions, all complexes show high rate enhancements due to the cooperative action of the Cu(II) ions. The kinetics indicate for 3-Cu-2 bifunctional catalytic effects. At the pH optimum of 7.4 at least one amine is protonated, which can assist as a general acid in the binding and activation of the substrate.

  DOI：

  10.1021/jo9905266

文献信息

• Dinuclear Bisimidazolyl-Cu(II) Calix[4]arenes as Metalloenzyme Models. Synthesis and Bifunctional Catalysis in Phosphate Diester Transesterification
  作者：Peter Molenveld、Johan F. J. Engbersen、David N. Reinhoudt

  DOI：10.1021/jo9905266

  日期：1999.8.1

  Calix[4]arenes functionalized with two catalytic bisimidazolyl-Cu(II) centers and two additional hydroxymethyl (2-Cu-2) or aminomethyl groups (3-Cu-2) were synthesized as models for enzymes that cleave phosphate diester bonds. The kinetics of 2-Cu-2 and 3-Cu-2 in the catalysis of the intramolecular transesterification of the RNA model substrate 2-hydroxypropyl-p-nitrophenyl phosphate were compared with those of the parent calix[4]arene 1-Cu-2, lacking the two additional functional groups. Under neutral conditions, all complexes show high rate enhancements due to the cooperative action of the Cu(II) ions. The kinetics indicate for 3-Cu-2 bifunctional catalytic effects. At the pH optimum of 7.4 at least one amine is protonated, which can assist as a general acid in the binding and activation of the substrate.