2-benzyl-4β-ethyl-6-oxo-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<4,3-b>indole | 128902-22-7

• 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-benzyl-4β-ethyl-6-oxo-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<4,3-b>indole
• 英文别名: 2-benzyl-4α-ethyl-6-oxo-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<4,3-b>indole；2-benzyl-4-ethyl-6-oxo-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<4,3-b>indole；2-benzyl-4-ethyl-6-oxo-1,2,3,4,5,6-hexahydro-1,5-methanoazocino[4,3-b]indole
• CAS: 128902-22-7；128948-94-7
• 化学式: C₂₃H₂₄N₂O
• 分子量: 344.456
• InChiKey: UWWSZTHTNTUOFO-WNPSOCMYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.95
• 重原子数：
  26.0
• 可旋转键数：
  3.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  36.1
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  2-benzyl-4β-ethyl-6-oxo-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<4,3-b>indole 在 palladium dihydroxide lithium aluminium tetrahydride 、 Raney Ni (W-2) 、 三氟化硼乙醚 、 dimethyl(methylthio)sulfonium tetrafluoroborate 、 氢气 、 sodium hydride 、 sodium carbonate 作用下， 以 1,4-二氧六环 、 甲醇 、 乙醇 、 二氯甲烷 为溶剂， 反应 88.75h， 生成 (-)-19,20-dihydroakuammicine
  参考文献：
  名称：

  A new synthetic entry to pentacyclic Strychnos alkaloids. Total synthesis of (.+-.)-tubifolidine, (.+-.)-tubifoline, and (.+-.)-19,20-dihydroakuammicine

  摘要：

  A new strategy for the synthesis of pentacyclic Strychnos alkaloids has been developed. It consists in the closure of the five-membered E ring by cyclization upon the indole 3-position from a suitably N-substituted tetracyclic system embodying rings ABCD of the alkaloids. Attempts to effect the key cyclization either by Pummerer rearrangement of sulfinylacetamides 4 and 6, from chloroacetamide 12, or from bis(methylthio)acetamide 10b (exocyclic amide carbonyl group) resulted in failure. In the first case dithioacetals 9 and 10, respectively, were formed in good yields. Cyclization from alcohol 13 or from the indole-deactivated acetal 15 and dithiocetal 18 were also unsuccessful: noncyclized products coming from the initially formed oxonium or thionium intermediates 16 were obtained. Cyclization was satisfactorily accomplished in 49% yield by treatment of the N-unsubstituted indole dithioacetal 23 with DMTSF. The resulting pentacycle 25 was converted to 20-deethyltubifolidine (27). A similar treatment from dithioacetal 41a, prepared from the secondary amine 32a, afforded pentacycle 42a, from which the alkaloids tubifoline, tubifolidine, and 19,20-dihydroakuammicine were synthesized.

  DOI：

  10.1021/jo00313a017
• 作为产物：
  描述：

  methyl 1-benzyl-5-ethyl-2-(1H-indol-3-yl)piperidine-4-carboxylate 在 barium dihydroxide 作用下， 以 1,4-二氧六环 为溶剂， 反应 25.0h， 生成 2-benzyl-4β-ethyl-6-oxo-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<4,3-b>indole
  参考文献：
  名称：

  A new synthetic entry to pentacyclic Strychnos alkaloids. Total synthesis of (.+-.)-tubifolidine, (.+-.)-tubifoline, and (.+-.)-19,20-dihydroakuammicine

  摘要：

  A new strategy for the synthesis of pentacyclic Strychnos alkaloids has been developed. It consists in the closure of the five-membered E ring by cyclization upon the indole 3-position from a suitably N-substituted tetracyclic system embodying rings ABCD of the alkaloids. Attempts to effect the key cyclization either by Pummerer rearrangement of sulfinylacetamides 4 and 6, from chloroacetamide 12, or from bis(methylthio)acetamide 10b (exocyclic amide carbonyl group) resulted in failure. In the first case dithioacetals 9 and 10, respectively, were formed in good yields. Cyclization from alcohol 13 or from the indole-deactivated acetal 15 and dithiocetal 18 were also unsuccessful: noncyclized products coming from the initially formed oxonium or thionium intermediates 16 were obtained. Cyclization was satisfactorily accomplished in 49% yield by treatment of the N-unsubstituted indole dithioacetal 23 with DMTSF. The resulting pentacycle 25 was converted to 20-deethyltubifolidine (27). A similar treatment from dithioacetal 41a, prepared from the secondary amine 32a, afforded pentacycle 42a, from which the alkaloids tubifoline, tubifolidine, and 19,20-dihydroakuammicine were synthesized.

  DOI：

  10.1021/jo00313a017