5,9,12-trimethyl-6,7,8,9,10,11-hexahydro-8,9-<(1-acetylethylene)oxy>-6,10-imino-5H-cyclooctindole | 123241-31-6

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 大灵碱生物碱
• 英文名称: 5,9,12-trimethyl-6,7,8,9,10,11-hexahydro-8,9-<(1-acetylethylene)oxy>-6,10-imino-5H-cyclooctindole
• 英文别名: 5,9,12-trimethyl-6,7,8,9,10,11-hexahydro-8,9-[(1-acetylethylene)oxy]-6,10-imino-5H-cyclooct[b]indole
• CAS: 123241-31-6
• 化学式: C₂₁H₂₄N₂O₂
• 分子量: 336.434
• InChiKey: SZTHOIQVKZYFAC-MCNSAMFCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.36
• 重原子数：
  25.0
• 可旋转键数：
  1.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  34.47
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  (6S,10S)-(-)-5,12-dimethyl-9-<<(3-oxo-1-(E)-butenyl)oxy>methyl>-6,7,10,11-tetrahydro-6,10-imino-5H-cyclooctindole 以 苯 为溶剂， 反应 40.0h， 生成 5,9,12-trimethyl-6,7,8,9,10,11-hexahydro-8,9-<(1-acetylethylene)oxy>-6,10-imino-5H-cyclooctindole
  参考文献：
  名称：

  Enantiospecific Synthesis of (-)-Alstonerine and (+)-Macroline as Well as a Partial Synthesis of (+)-Villalstonine

  摘要：

  The enantiospecific synthesis of (-)-alstonerine (5) and (+)-macroline (8), as well as a partial synthesis of the Alstonia bisindole alkaloid villalstonine (2) has been completed. In addition, a more stable macroline equivalent 9 was prepared. The stereochemistry at C(15) and C(16) in 5 and 8 has been successfully installed by a stereoselective Claisen rearrangement followed by stereospecific hydroboration-oxidation of the exocyclic methylene function at C-16. The E ring in alstonerine 5 was constructed by a regioselective cyclization followed by a novel Swern oxidation under modified conditions [(COCl)(2)/DMSO/CH2Cl2, -78 degrees C to -10 degrees C/1.5 h; Et(3)N], whereas the C(20)-C(21) enone system in macroline (8) was generated via a convenient one pot process from the beta-diol 45. Condensation of either synthetic (+)-macroline (8) or the macroline equivalent 9 with natural pleiocarpamine 7 in 0.2 N HCl furnished the antiamoebic, antimalarial bisindole alkaloid villalstonine 2. This constitutes the first partial synthesis of any of the Alstonia bisindoles from a synthetically derived indole moiety.

  DOI：

  10.1021/ja00099a021

文献信息

• [3,3]-Sigmatropic rearrangements in indoloazabicyclo[3.3.1]nonene systems. Reversal of the stereofacial selectivity in the Claisen vs. the ortho ester Claisen rearrangement
  作者：Lin Hua Zhang、Mark L. Trudell、Sean P. Hollinshead、James M. Cook

  DOI：10.1021/ja00203a030

  日期：1989.10