2-benzyl-4α-ethyl-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<4,3-b>indole | 128948-95-8

• 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-4α-ethyl-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<4,3-b>indole
• 英文别名: 2-benzyl-4α-ethyl-1,2,3,4,5,6-hexahydro-1,5-methanoazocino[4,3-b]indole；(1S,12R,13R)-15-benzyl-13-ethyl-9,15-diazatetracyclo[10.3.1.02,10.03,8]hexadeca-2(10),3,5,7-tetraene
• CAS: 128948-95-8
• 化学式: C₂₃H₂₆N₂
• 分子量: 330.473
• InChiKey: SMCAERLGGLRGIW-SPEDKVCISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.31
• 重原子数：
  25.0
• 可旋转键数：
  3.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  19.03
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  2-benzyl-4α-ethyl-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<4,3-b>indole 在 palladium dihydroxide dimethyl(methylthio)sulfonium tetrafluoroborate 、 氢气 、 sodium citrate 、 sodium cyanoborohydride 、 柠檬酸 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 75.0h， 生成 6α-(methylthio)-20-epitubifoline
  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：

  t-4-Acetonyl-1-benzyl-c-5-ethyl-r-2-piperidinecarbonitrile 在 盐酸 作用下， 以 甲醇 、 乙醇 为溶剂， 反应 60.5h， 生成 2-benzyl-4α-ethyl-1,2,3,4,5,6-hexahydro-1,5-methanoazocino<4,3-b>indole
  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