13,15,16,18-Tetrakis(tert-butoxycarbonyl)tricyclo<10.3.3.0^1,12>octadecane-14,17-dione | 130156-18-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 13,15,16,18-Tetrakis(tert-butoxycarbonyl)tricyclo<10.3.3.0^1,12>octadecane-14,17-dione
• CAS: 130156-18-2
• 化学式: C₃₈H₆₀O₁₀
• 分子量: 676.888
• InChiKey: GWOXWSOLIZVTOX-VKZTVEQXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.12
• 重原子数：
  48.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  145.66
• 氢给体数：
  2.0
• 氢受体数：
  10.0

反应信息

• 作为反应物：
  描述：

  重氮甲烷 、 13,15,16,18-Tetrakis(tert-butoxycarbonyl)tricyclo<10.3.3.0^1,12>octadecane-14,17-dione 以 乙醚 为溶剂， 以95%的产率得到13,15,16,18-Tetrakis(tert-butoxycarbonyl)-14,17-dimethoxytricyclo<10.3.3.0^1,12>octadeca-13,16-diene
  参考文献：
  名称：

  General approach for the synthesis of polyquinenes via the Weiss reaction. 14. Synthesis of ellacene (1,10-decanotriquinacene) and studies of the proposed dimerization to a substituted dodecahedrane

  摘要：

  Ellacene 4, a tetracyclic 1,10-centrosubstituted triquinacene, has been synthesized via the Weiss reaction. The condensation of cyclododecane-1,2-dione (5) with di-tert-butyl 3-ketoglutarate (6) under aqueous alkaline conditions provided 13,15,16,18-tetrakis(tert-butoxycarbonyl)tricyclo[10.3.3.0(1,12)]octadecane-14,17-dione in the bisenol form 7 in 85 % yield. The bisenol ether 8 was regioselectively monoalkylated to furnish in 96 % yield the monoallyl ester 9 which was hydrolyzed to provide 13-allyltricyclo[10.3.3.0(1,12)]octadecane-14,17-dione (10). Intramolecular aldol reaction of the related diketo aldehyde 11 to furnish 17-hydroxytetracyclo[11.5.2.0(2,13).0(2,16)]eicosane-15,19-dione (12) was carried out under aqueous acidic conditions. The Lewis acid mediated (BH3/THF) reduction of the diketo alcohol provided the corresponding triol 13 in excellent yield. Conversion of the triol into the trisxanthate 21 followed by syn elimination (HMPA, 220-degrees-C) provided the desired triene 4 in 91 % yield. Attempted dimerization of 4 (ellacene) to a substituted dodecahedrane 3 under photochemical conditions and/or high pressure (130 kbar) has failed to generate 3 to date under conditions that did effect [2 + 2] dimerization of the parent, triquinacene.

  DOI：

  10.1021/jo00045a023
• 作为产物：
  描述：

  cyclododecane-1,2-dione 、 3-氧化戊二酸二叔丁酯 在 碳酸氢钠 、 potassium carbonate 作用下， 以 甲醇 为溶剂， 以85%的产率得到13,15,16,18-Tetrakis(tert-butoxycarbonyl)tricyclo<10.3.3.0^1,12>octadecane-14,17-dione
  参考文献：
  名称：

  General approach for the synthesis of polyquinenes via the Weiss reaction. 14. Synthesis of ellacene (1,10-decanotriquinacene) and studies of the proposed dimerization to a substituted dodecahedrane

  摘要：

  Ellacene 4, a tetracyclic 1,10-centrosubstituted triquinacene, has been synthesized via the Weiss reaction. The condensation of cyclododecane-1,2-dione (5) with di-tert-butyl 3-ketoglutarate (6) under aqueous alkaline conditions provided 13,15,16,18-tetrakis(tert-butoxycarbonyl)tricyclo[10.3.3.0(1,12)]octadecane-14,17-dione in the bisenol form 7 in 85 % yield. The bisenol ether 8 was regioselectively monoalkylated to furnish in 96 % yield the monoallyl ester 9 which was hydrolyzed to provide 13-allyltricyclo[10.3.3.0(1,12)]octadecane-14,17-dione (10). Intramolecular aldol reaction of the related diketo aldehyde 11 to furnish 17-hydroxytetracyclo[11.5.2.0(2,13).0(2,16)]eicosane-15,19-dione (12) was carried out under aqueous acidic conditions. The Lewis acid mediated (BH3/THF) reduction of the diketo alcohol provided the corresponding triol 13 in excellent yield. Conversion of the triol into the trisxanthate 21 followed by syn elimination (HMPA, 220-degrees-C) provided the desired triene 4 in 91 % yield. Attempted dimerization of 4 (ellacene) to a substituted dodecahedrane 3 under photochemical conditions and/or high pressure (130 kbar) has failed to generate 3 to date under conditions that did effect [2 + 2] dimerization of the parent, triquinacene.

  DOI：

  10.1021/jo00045a023