(1RS,4RS,5SR)-4-Ethyl-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<4,3-b>indole | 116965-63-0

• 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: (1RS,4RS,5SR)-4-Ethyl-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<4,3-b>indole
• 英文别名: 4α-ethyl-1,2,3,4,5,6-hexahidro-1,5-methanoazocino<4,3-b>indole；4α-ethyl-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<4,3-b>indole；4α-ethyl-1,2,3,4,5,6-hexahydro-1,5-methanoazocino[4,3-b]indole；(1R,12S,13S)-13-ethyl-9,15-diazatetracyclo[10.3.1.02,10.03,8]hexadeca-2(10),3,5,7-tetraene
• CAS: 116965-63-0
• 化学式: C₁₆H₂₀N₂
• 分子量: 240.348
• InChiKey: HNNBYWBOXFVPDZ-UHIISALHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  27.8
• 氢给体数：
  2
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1RS,4RS,5SR)-4-Ethyl-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<4,3-b>indole 在 10% palladium on active carbon selenium(IV) oxide 、 氢气 、 potassium carbonate 作用下， 以 1,4-二氧六环 、 甲醇 、 氯仿 为溶剂， 反应 185.5h， 生成 (+/-)-Isodasycarpidone
  参考文献：
  名称：

  Total Synthesis of Uleine-Type and Strychnos Alkaloids through a Common Intermediate

  摘要：

  A stereoselective total synthesis of the alkaloids of the uleine group, dasycarpidone, dasycarpidol, and nordasycarpidone, has been accomplished from the tetracyclic intermediate 1, which has been prepared by two alternative routes, either by Fischer indolization of 2-azabicyclo[3.3.1]nonanone 9 or, more efficiently, by stereocontrolled cyclization of 2-[(2-cyano-3-ethyl-4-piperidyl)methyl]i 24a and 24b. From the same tetracyclic intermediate 1, the Strychnos alkaloid tubotaiwine was also synthesized, the key step being the construction of the quaternary spiranic center by cyclization of a thionium ion upon the indole beta-position.

  DOI：

  10.1021/jo00093a028
• 作为产物：
  描述：

  2-benzyl-4α-ethyl-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<4,3-b>indole 在 palladium dihydroxide 氢气 作用下， 以 甲醇 为溶剂， 以71%的产率得到(1RS,4RS,5SR)-4-Ethyl-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

文献信息

• A new strategy for the synthesis of pentacyclic Strychnos alkaloids: synthesis of (±)-tubifolidine
  作者：Mercedes Amat、Ana Linares、M.-Luisa Salas、Mercedes Alvarez、Joan Bosch

  DOI：10.1039/c39880000420

  日期：——

  The hexahydro-1,5-methanoazocino[4,3-b]indole (2a) was converted into (±)-tubifolidine (6a)via a four-step synthetic sequence which involves cyclization of a thionium ion upon the 3-position of a 2,3-disubstituted indole as the crucial step.

  通过四步合成序列将六氢-1,5-甲亚氮并吲哚并[4,3- b ]吲哚（2a）转化为（±）-tubifolidine（6a），该过程涉及在硫醇离子的3位上环化硫鎓离子。 2,3-二取代的吲哚是关键步骤。
• Enantiopure intermediates for the synthesis of Strychnos alkaloids
  作者：Mercedes Amat、Ma Dolors Coll、Joan Bosch

  DOI：10.1016/0040-4020(95)00641-k

  日期：1995.9

  The addition of 2-(lithiomethyl)indole 2 to the enantiopure oxazolinylpyridine 18 followed by acidic treatment afforded a mixture of tetracyclic compounds 21a and 21b in a 3:2 ratio. The major epimer 21a was converted to tetracycle 25a, a tetracyclic ABDE substructure of Strychnos alkaloids.
• A new synthetic entry to pentacyclic Strychnos alkaloids. Total synthesis of (.+-.)-tubifolidine, (.+-.)-tubifoline, and (.+-.)-19,20-dihydroakuammicine
  作者：Mercedes Amat、Ana Linares、Joan Bosch

  DOI：10.1021/jo00313a017

  日期：1990.12

  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.
• Total Synthesis of Uleine-Type and Strychnos Alkaloids through a Common Intermediate
  作者：Jordi Gracia、Nuria Casamitjana、Josep Bonjoch、Joan Bosch

  DOI：10.1021/jo00093a028

  日期：1994.7

  A stereoselective total synthesis of the alkaloids of the uleine group, dasycarpidone, dasycarpidol, and nordasycarpidone, has been accomplished from the tetracyclic intermediate 1, which has been prepared by two alternative routes, either by Fischer indolization of 2-azabicyclo[3.3.1]nonanone 9 or, more efficiently, by stereocontrolled cyclization of 2-[(2-cyano-3-ethyl-4-piperidyl)methyl]i 24a and 24b. From the same tetracyclic intermediate 1, the Strychnos alkaloid tubotaiwine was also synthesized, the key step being the construction of the quaternary spiranic center by cyclization of a thionium ion upon the indole beta-position.