Tetracyclo<11.5.2.0^2,13.0^2,16>eicosane-15,17,19-trione | 143065-28-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Tetracyclo<11.5.2.0^2,13.0^2,16>eicosane-15,17,19-trione
• 英文别名: (1S,12R,13R,16R)-tetracyclo[11.5.2.01,12.012,16]icosane-14,17,20-trione
• CAS: 143065-28-5
• 化学式: C₂₀H₂₈O₃
• 分子量: 316.441
• InChiKey: AINKXRJKTIKTQR-WEFJBSGNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  23
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  51.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Tetracyclo<11.5.2.0^2,13.0^2,16>eicosane-15,17,19-trione 、 对甲苯磺酰肼 在 盐酸 作用下， 以 乙醇 为溶剂， 反应 4.0h， 以70%的产率得到Tetracyclo<11.5.2.0^2,13.0^2,16>eicosane-15,17,19-trione tris(tosylhydrazone)
  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：

  17-Hydroxytetracyclo<11.5.2.0^2,13.0^2,16>eicosane-15,19-dione 在 Celite 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 18.0h， 以96%的产率得到Tetracyclo<11.5.2.0^2,13.0^2,16>eicosane-15,17,19-trione
  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