2,2,2-trichloro-N-[2-(1H-indol-3-yl)ethyl]-N-(4-oxocyclohexyl)acetamide | 171367-15-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: 2,2,2-trichloro-N-[2-(1H-indol-3-yl)ethyl]-N-(4-oxocyclohexyl)acetamide
• CAS: 171367-15-0
• 化学式: C₁₈H₁₉Cl₃N₂O₂
• 分子量: 401.72
• InChiKey: DRZQOOUWEHQRKX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  53.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,2,2-trichloro-N-[2-(1H-indol-3-yl)ethyl]-N-(4-oxocyclohexyl)acetamide 在 吡啶 、 sodium tetrahydroborate 、 偶氮二异丁腈 、 三(三甲基硅基)硅烷 、 zinc(II) iodide 、 三氯氧磷 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 12.75h， 生成 (2RS,3RS,6SR,14bSR)-2,3,4,5,6,7,8,9,14,14b-decahydro-2,6-methano-1H-azocino[1',2':1,2]pyrido[3,4-b]indole-3-carbonitrile
  参考文献：
  名称：

  First Total Synthesis of (±)-Melinonine-E and (±)-Strychnoxanthine Using a Radical Cyclization Process as the Core Ring-Forming Step

  摘要：

  The first total synthesis of (+/-)-melinonine-E and (+/-)-strychnoxanthine is described. The key common step for the synthesis of both alkaloids is the elaboration of the 8-azabicyclo[3.3.1]nonane nucleus (D and E rings) by a radical carbocyclization, using an alpha-carbamoyldichloromethyl radical as a donor. The closure of the C ring by a Bischler-Napieralski cyclization, followed by an epimerization process to gain the axial nitrile 20, and appropriate reduction transformations afforded pentacyclic alcohol 23. This alcohol was converted into either (+/-)-melinonine-E (1) or (+/-)-strychnoxanthine (2) by means of a palladium black dehydrogenation of the C ring or a SeO2 oxidation of the corresponding acetate 25, respectively.

  DOI：

  10.1021/jo971148c
• 作为产物：
  描述：

  1,4-环己二酮单乙二醇缩酮 在 吡啶 、 盐酸 、 三乙酰氧基硼氢化钠 、 溶剂黄146 作用下， 以 四氢呋喃 、 二氯甲烷 、 1,2-二氯乙烷 为溶剂， 反应 41.0h， 生成 2,2,2-trichloro-N-[2-(1H-indol-3-yl)ethyl]-N-(4-oxocyclohexyl)acetamide
  参考文献：
  名称：

  First Total Synthesis of (±)-Melinonine-E and (±)-Strychnoxanthine Using a Radical Cyclization Process as the Core Ring-Forming Step

  摘要：

  The first total synthesis of (+/-)-melinonine-E and (+/-)-strychnoxanthine is described. The key common step for the synthesis of both alkaloids is the elaboration of the 8-azabicyclo[3.3.1]nonane nucleus (D and E rings) by a radical carbocyclization, using an alpha-carbamoyldichloromethyl radical as a donor. The closure of the C ring by a Bischler-Napieralski cyclization, followed by an epimerization process to gain the axial nitrile 20, and appropriate reduction transformations afforded pentacyclic alcohol 23. This alcohol was converted into either (+/-)-melinonine-E (1) or (+/-)-strychnoxanthine (2) by means of a palladium black dehydrogenation of the C ring or a SeO2 oxidation of the corresponding acetate 25, respectively.

  DOI：

  10.1021/jo971148c

文献信息

• First total synthesis of (±)-melinonine-E
  作者：Josefina Quirante、Carmen Escolano、Joan Bosch、Josep Bonjoch

  DOI：10.1039/c39950002141

  日期：——

  The alkaloid melinonine-E has been synthesised for the first time, the key steps being the elaboration of the 2-azabicyclo[3.3.l]nonane nucleus by a radical cyclisation, the epimerisation of the cyano group to an axial position, and the closure of the C ring by Bischler–Napieralski cyclisation.

  首次合成了生物碱 Melinonine-E，其关键步骤是通过自由基环化法合成 2-氮杂双环[3.3.l]壬烷核、氰基环化至轴向位置以及通过比施勒-纳皮拉尔斯基环化法封闭 C 环。
• Radical promoted cyclisations of trichloroacetamides with silyl enol ethers and enol acetates: the role of the hydride reagent [tris(trimethylsilyl)silane vs. tributylstannane]
  作者：Josefina Quirante、Carmen Escolano、Faïza Diaba、Josep Bonjoch

  DOI：10.1039/a900952c

  日期：——

  Reactions between 1-(carbamoyl)dichloromethyl radicals and electron-rich alkenes acting as radical acceptors are reported for the first time. The intramolecular reaction of trichloroacetamides with silyl enol ethers gives ketones using (TMS)3SiH as the mediator, and alcohols when using Bu3SnH. The reaction with enol acetates gives acetates using either of the above hydride reagents. These radical processes have been applied to the synthesis of 2-azabicyclo[3.3.1]nonanes.

  首次报道了 1-(氨基甲酰基)二氯甲基自由基与作为自由基受体的富电子烯烃之间的反应。以 (TMS)3SiH 为媒介，三氯乙酰胺与硅基烯醚发生分子内反应，生成酮；以 Bu3SnH 为媒介，生成醇。使用上述任一种氢化物试剂与烯醇乙酸酯反应可生成乙酸酯。这些自由基过程已被用于合成 2-氮杂双环[3.3.1]壬烷。
• Cyclization of 1-(carbamoyl)dichloromethyl radicals upon activated alkenes. A new entry to 2-azabicyclo[3.3.1]nonanes
  作者：Josefina Quirante、Carmen Escolano、Laura Costejà、Josep Bonjoch

  DOI：10.1016/s0040-4039(97)01590-6

  日期：1997.9

  The synthesis of 2-azabicyclo[3.3.1]nonanes using a radical cyclization process as the piperidine ring-forming step is described. The reaction involves 1-(carbamoyl)-dichloromethyl radicals which react intramolecularly with simple or activated alkenes, such as enol acetates or silyl enol ethers.

  描述了使用自由基环化方法作为哌啶环形成步骤的2-氮杂双环[3.3.1]壬烷的合成。该反应涉及1-（氨基甲酰基）-二氯甲基基团，它们与简单或活化的烯烃，例如烯醇乙酸酯或甲硅烷基烯醇醚在分子内反应。
• First Total Synthesis of (±)-Melinonine-E and (±)-Strychnoxanthine Using a Radical Cyclization Process as the Core Ring-Forming Step
  作者：Josefina Quirante、Carmen Escolano、Alma Merino、Josep Bonjoch

  DOI：10.1021/jo971148c

  日期：1998.2.1

  The first total synthesis of (+/-)-melinonine-E and (+/-)-strychnoxanthine is described. The key common step for the synthesis of both alkaloids is the elaboration of the 8-azabicyclo[3.3.1]nonane nucleus (D and E rings) by a radical carbocyclization, using an alpha-carbamoyldichloromethyl radical as a donor. The closure of the C ring by a Bischler-Napieralski cyclization, followed by an epimerization process to gain the axial nitrile 20, and appropriate reduction transformations afforded pentacyclic alcohol 23. This alcohol was converted into either (+/-)-melinonine-E (1) or (+/-)-strychnoxanthine (2) by means of a palladium black dehydrogenation of the C ring or a SeO2 oxidation of the corresponding acetate 25, respectively.