[(3R,3aS,7aS)-3a-(3,4-dimethoxyphenyl)-1-(4-methylphenyl)sulfonyl-6-oxo-2,3,7,7a-tetrahydroindol-3-yl]methyl methyl carbonate | 189364-00-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [(3R,3aS,7aS)-3a-(3,4-dimethoxyphenyl)-1-(4-methylphenyl)sulfonyl-6-oxo-2,3,7,7a-tetrahydroindol-3-yl]methyl methyl carbonate
• CAS: 189364-00-9
• 化学式: C₂₆H₂₉NO₈S
• 分子量: 515.584
• InChiKey: GULDFQUCFNGEPS-YZXAJQSBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  36
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  117
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  [(3R,3aS,7aS)-3a-(3,4-dimethoxyphenyl)-1-(4-methylphenyl)sulfonyl-6-oxo-2,3,7,7a-tetrahydroindol-3-yl]methyl methyl carbonate 在 palladium on activated charcoal 三氟甲磺酸三甲基硅酯 、 RhCl(PPh₃)3 、 氢气 、 potassium carbonate 、 戴斯-马丁氧化剂 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 37.5h， 生成 松叶菊碱提取物
  参考文献：
  名称：

  Total Syntheses of (−)-Mesembrane and (−)-Mesembrine via Palladium-Catalyzed Enantioselective Allylic Substitution and Zirconium-Promoted Cyclization

  摘要：

  4-Arylhexahydroindole derivatives 5 were synthesized from 2-arylcyclohexenyl allylamine derivatives 4, which have a large protecting group on nitrogen, using zirconium-promoted cyclization. Reaction of 4e with Cp2ZrBu2, followed by treatment with MeMgBr and then O-2, gave 2a in 63% yield by a one-pot reaction, since the approach of Oz to zirconium was prevented by the aryl group. The total syntheses of (+/-)-mesembrane and (+/-)-mesembrine were achieved starting from 2a. To synthesize these natural products in a chiral form, the starting allylamine derivative 24 (80% yield, 86% ee, recrystallized from MeOH, 99% ee with 79% recovery) was prepared from allyl carbonate 22a and N-tosylallylamine 23 using palladium-catalyzed asymmetric amination in the presence of (S)-BINAPO as a chiral ligand. (-)-Mesembrane and (-)-mesembrine were synthesized from this allylamine 24.

  DOI：

  10.1021/jo9701187
• 作为产物：
  描述：

  2-bromocyclohex-2-en-1-ol 在 palladium on activated charcoal 吡啶 、 咪唑 、 3,5-二甲基吡唑 、 chromium(VI) oxide 、 四(三苯基膦)钯 、 四溴化碳 、 四丁基氟化铵 、 氢气 、 双氧水 、 sodium carbonate 、 potassium carbonate 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 270.8h， 生成 [(3R,3aS,7aS)-3a-(3,4-dimethoxyphenyl)-1-(4-methylphenyl)sulfonyl-6-oxo-2,3,7,7a-tetrahydroindol-3-yl]methyl methyl carbonate
  参考文献：
  名称：

  Total Syntheses of (−)-Mesembrane and (−)-Mesembrine via Palladium-Catalyzed Enantioselective Allylic Substitution and Zirconium-Promoted Cyclization

  摘要：

  4-Arylhexahydroindole derivatives 5 were synthesized from 2-arylcyclohexenyl allylamine derivatives 4, which have a large protecting group on nitrogen, using zirconium-promoted cyclization. Reaction of 4e with Cp2ZrBu2, followed by treatment with MeMgBr and then O-2, gave 2a in 63% yield by a one-pot reaction, since the approach of Oz to zirconium was prevented by the aryl group. The total syntheses of (+/-)-mesembrane and (+/-)-mesembrine were achieved starting from 2a. To synthesize these natural products in a chiral form, the starting allylamine derivative 24 (80% yield, 86% ee, recrystallized from MeOH, 99% ee with 79% recovery) was prepared from allyl carbonate 22a and N-tosylallylamine 23 using palladium-catalyzed asymmetric amination in the presence of (S)-BINAPO as a chiral ligand. (-)-Mesembrane and (-)-mesembrine were synthesized from this allylamine 24.

  DOI：

  10.1021/jo9701187

文献信息

• Total Syntheses of (−)-Mesembrane and (−)-Mesembrine <i>via</i> Palladium-Catalyzed Enantioselective Allylic Substitution and Zirconium-Promoted Cyclization
  作者：Miwako Mori、Shinji Kuroda、Chang-Shan Zhang、Yoshihiro Sato

  DOI：10.1021/jo9701187

  日期：1997.5.1

  4-Arylhexahydroindole derivatives 5 were synthesized from 2-arylcyclohexenyl allylamine derivatives 4, which have a large protecting group on nitrogen, using zirconium-promoted cyclization. Reaction of 4e with Cp2ZrBu2, followed by treatment with MeMgBr and then O-2, gave 2a in 63% yield by a one-pot reaction, since the approach of Oz to zirconium was prevented by the aryl group. The total syntheses of (+/-)-mesembrane and (+/-)-mesembrine were achieved starting from 2a. To synthesize these natural products in a chiral form, the starting allylamine derivative 24 (80% yield, 86% ee, recrystallized from MeOH, 99% ee with 79% recovery) was prepared from allyl carbonate 22a and N-tosylallylamine 23 using palladium-catalyzed asymmetric amination in the presence of (S)-BINAPO as a chiral ligand. (-)-Mesembrane and (-)-mesembrine were synthesized from this allylamine 24.