(+/-)-methyl (2S*,5R*,11bR*)-3-((phenylthio)methyl)-2,3,3a,4,5,7-hexahydro-5-(1-propionyl)-1H-pyrrolo<2,3-d>carbazole-6-carboxylate

• 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: (+/-)-methyl (2S*,5R*,11bR*)-3-((phenylthio)methyl)-2,3,3a,4,5,7-hexahydro-5-(1-propionyl)-1H-pyrrolo<2,3-d>carbazole-6-carboxylate
• 英文别名: methyl (3aS,5R,11bR)-3-(phenylsulfanylmethyl)-5-propanoyl-1,2,3a,4,5,7-hexahydropyrrolo[2,3-d]carbazole-6-carboxylate
• 化学式: C₂₆H₂₈N₂O₃S
• 分子量: 448.586
• InChiKey: WHIAKXFFWOFJOX-HBTLOVQCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  83.9
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (+/-)-methyl (2S*,5R*,11bR*)-3-((phenylthio)methyl)-2,3,3a,4,5,7-hexahydro-5-(1-propionyl)-1H-pyrrolo<2,3-d>carbazole-6-carboxylate 在 三正丁基氢锡 作用下， 以 苯 为溶剂， 反应 1.0h， 以72%的产率得到(+/-)-methyl (2S*,5R*,11bR*)-3-methyl-2,3,3a,4,5,7-hexahydro-5-(1-propionyl)-1H-pyrrolo<2,3-d>carbazole-6-carboxylate
  参考文献：
  名称：

  Syntheses of Strychnan- and Aspidospermatan-Type Alkaloids. 11. Total Syntheses of (−)-Lochneridine and (−)- and Racemic 20-epi-Lochneridine

  摘要：

  Enantioselective syntheses of (-)-lochneridine (1) and (-)-epi-lochneridine (2) were obtained by two alternative C-20 diastereoselective syntheses of the respective pentacyclic (3aS,5S,11bR)-methyl 12-oxo-3,5-ethano-2,3,3a,4,5,7-hexahydro-3H-pyrrolo[2,3-d]carbazole-6-carboxylate ((-)-8) and tetracyclic methyl (2S,3aS,5R,11bR))-3-benzyl-2,3,3a,4,5,7-hexahydro-5-(2-(1-butenyl))-1H-pyrrolo[2,3d]carbazole-6-carboxylate ((-)-12b) precursors from tryptophan derived 2-[(methoxycarbonyl)methyl]3-[2(S)-(methoxy or benzyloxycarbonyl)-2-(N-b-benzyl)aminoethyl]indole (15 or 16). While a modified Grignard reaction of the ketone (-)-8 provided (-)-lochneridine (1), dihydroxylation and cyclization of the olefin (-)-12b gave its C-20 epimer (2).

  DOI：

  10.1021/jo981401o
• 作为产物：
  描述：

  (+/-)-methyl (2S*,3aS*,5R*,11bR*)-3-benzyl-2,3,3a,4,5,7-hexahydro-5-formyl-1H-pyrrolo<2,3-d>carbazole-6-carboxylate 在 palladium on activated charcoal N-氯代丁二酰亚胺 、 二甲基硫 、 氢气 、 甲酸铵 、 sodium carbonate 、 sodium iodide 作用下， 以 四氢呋喃 、 吡啶 、 甲醇 、 乙醚 、 甲苯 为溶剂， 反应 7.0h， 生成 (+/-)-methyl (2S*,5R*,11bR*)-3-((phenylthio)methyl)-2,3,3a,4,5,7-hexahydro-5-(1-propionyl)-1H-pyrrolo<2,3-d>carbazole-6-carboxylate
  参考文献：
  名称：

  Syntheses of Strychnan- and Aspidospermatan-Type Alkaloids. 11. Total Syntheses of (−)-Lochneridine and (−)- and Racemic 20-epi-Lochneridine

  摘要：

  Enantioselective syntheses of (-)-lochneridine (1) and (-)-epi-lochneridine (2) were obtained by two alternative C-20 diastereoselective syntheses of the respective pentacyclic (3aS,5S,11bR)-methyl 12-oxo-3,5-ethano-2,3,3a,4,5,7-hexahydro-3H-pyrrolo[2,3-d]carbazole-6-carboxylate ((-)-8) and tetracyclic methyl (2S,3aS,5R,11bR))-3-benzyl-2,3,3a,4,5,7-hexahydro-5-(2-(1-butenyl))-1H-pyrrolo[2,3d]carbazole-6-carboxylate ((-)-12b) precursors from tryptophan derived 2-[(methoxycarbonyl)methyl]3-[2(S)-(methoxy or benzyloxycarbonyl)-2-(N-b-benzyl)aminoethyl]indole (15 or 16). While a modified Grignard reaction of the ketone (-)-8 provided (-)-lochneridine (1), dihydroxylation and cyclization of the olefin (-)-12b gave its C-20 epimer (2).

  DOI：

  10.1021/jo981401o