(5S*,8aR*)-1,2,3,5,6,7,8,8a-Octahydro-5<(dimethylphenylsilyl)methyl>-1-(methoxycarbonyl)-4-<(trifluoromethanesulfonyl)oxy>quinoline

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: (5S*,8aR*)-1,2,3,5,6,7,8,8a-Octahydro-5<(dimethylphenylsilyl)methyl>-1-(methoxycarbonyl)-4-<(trifluoromethanesulfonyl)oxy>quinoline
• 英文别名: methyl (5S,8aS)-5-[[dimethyl(phenyl)silyl]methyl]-4-(trifluoromethylsulfonyloxy)-3,5,6,7,8,8a-hexahydro-2H-quinoline-1-carboxylate
• 化学式: C₂₁H₂₈F₃NO₅SSi
• 分子量: 491.604
• InChiKey: QWUAZJNIXWIFME-WBVHZDCISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.36
• 重原子数：
  32
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  81.3
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (5S*,8aR*)-1,2,3,5,6,7,8,8a-Octahydro-5<(dimethylphenylsilyl)methyl>-1-(methoxycarbonyl)-4-<(trifluoromethanesulfonyl)oxy>quinoline 在 palladium on activated charcoal 氢气 、 lithium carbonate 作用下， 以 乙酸乙酯 为溶剂， 反应 48.0h， 以98%的产率得到(4aS*,5S*,8aR*)-1,2,3,4,4a,5,6,7,8,8a-Decahydro-5-<(dimethylphenylsilyl)methyl>-1-(methoxycarbonyl)quinoline
  参考文献：
  名称：

  Model Studies toward the Synthesis of the Lycopodium Alkaloid, Phlegmarine

  摘要：

  Model studies were carried out toward the preparation of Lycopodium alkaloids, i.e. the phlegmarines, which contain a trans-decahydroquinoline ring system, The target decahydroquinoline derivative 6 was synthesized stereoselectively in eight steps. The keto aldehyde 10, prepared in three steps from 4-methoxypyridine, was subjected to an acid-catalyzed Robinson annulation reaction to give bicyclic enone 11, Copper-mediated 1,4-addition of [(dimethylphenylsilyl)methyl]magnesium chloride and in situ trapping with N-(5-chloro-2-pyridyl)triflimide provided vinyl triflate 12. Conversion to olefin 16 and subsequent hydrolysis gave amine 20, Stereoselective hydrogenation of 20 over palladium on carbon yielded the trans-decahydroquinoline 6 and its cis isomer 21 in a ratio of 89:11, Arguments involving A((1,3)) strain are given to explain the observed stereoselectivity.

  DOI：

  10.1021/jo00108a039
• 作为产物：
  描述：

  4-甲氧基吡啶 在 对甲苯磺酸 二甲基硫 、 L-Selectride 、 臭氧 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 40.5h， 生成 (5S*,8aR*)-1,2,3,5,6,7,8,8a-Octahydro-5<(dimethylphenylsilyl)methyl>-1-(methoxycarbonyl)-4-<(trifluoromethanesulfonyl)oxy>quinoline
  参考文献：
  名称：

  Model Studies toward the Synthesis of the Lycopodium Alkaloid, Phlegmarine

  摘要：

  Model studies were carried out toward the preparation of Lycopodium alkaloids, i.e. the phlegmarines, which contain a trans-decahydroquinoline ring system, The target decahydroquinoline derivative 6 was synthesized stereoselectively in eight steps. The keto aldehyde 10, prepared in three steps from 4-methoxypyridine, was subjected to an acid-catalyzed Robinson annulation reaction to give bicyclic enone 11, Copper-mediated 1,4-addition of [(dimethylphenylsilyl)methyl]magnesium chloride and in situ trapping with N-(5-chloro-2-pyridyl)triflimide provided vinyl triflate 12. Conversion to olefin 16 and subsequent hydrolysis gave amine 20, Stereoselective hydrogenation of 20 over palladium on carbon yielded the trans-decahydroquinoline 6 and its cis isomer 21 in a ratio of 89:11, Arguments involving A((1,3)) strain are given to explain the observed stereoselectivity.

  DOI：

  10.1021/jo00108a039

文献信息

• Model Studies toward the Synthesis of the Lycopodium Alkaloid, Phlegmarine
  作者：Daniel L. Comins、Rima S. Al-awar

  DOI：10.1021/jo00108a039

  日期：1995.2

  Model studies were carried out toward the preparation of Lycopodium alkaloids, i.e. the phlegmarines, which contain a trans-decahydroquinoline ring system, The target decahydroquinoline derivative 6 was synthesized stereoselectively in eight steps. The keto aldehyde 10, prepared in three steps from 4-methoxypyridine, was subjected to an acid-catalyzed Robinson annulation reaction to give bicyclic enone 11, Copper-mediated 1,4-addition of [(dimethylphenylsilyl)methyl]magnesium chloride and in situ trapping with N-(5-chloro-2-pyridyl)triflimide provided vinyl triflate 12. Conversion to olefin 16 and subsequent hydrolysis gave amine 20, Stereoselective hydrogenation of 20 over palladium on carbon yielded the trans-decahydroquinoline 6 and its cis isomer 21 in a ratio of 89:11, Arguments involving A((1,3)) strain are given to explain the observed stereoselectivity.