(+/-)-Tubotaiwine

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 马钱子生物碱
• 英文名称: (+/-)-Tubotaiwine
• 英文别名: methyl (1R,11R,17S,18S)-18-ethyl-8,14-diazapentacyclo[9.5.2.01,9.02,7.014,17]octadeca-2,4,6,9-tetraene-10-carboxylate
• 化学式: C₂₀H₂₄N₂O₂
• 分子量: 324.423
• InChiKey: RLAKWLFUMAABBE-QLBVAGGCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  41.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  1-(1-苄基-4-哌啶基)丙-2-酮 在 palladium dihydroxide 盐酸 、 Raney Ni W-2 、 三氟化硼乙醚 、 dimethyl(methylthio)sulfonium tetrafluoroborate 、 氢气 、 sodium acetate 、 sodium hydride 、 sodium carbonate 、 间氯过氧苯甲酸 、 三氟乙酸酐 作用下， 以 1,4-二氧六环 、 甲醇 、 乙二醇二甲醚 、 乙醇 、 二氯甲烷 、 乙腈 为溶剂， 反应 197.5h， 生成 (+/-)-Tubotaiwine
  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

文献信息

• Total synthesis of the Strychnos alkaloid tubotaiwine
  作者：Jordi Gràcia、Josep Bonjoch、Núria Casamitjana、Mercedes Amat、Joan Bosch

  DOI：10.1039/c39910000614

  日期：——

  The total synthesis of racemic tubotaiwine 8 has been achieved from the tetracyclic intermediate 1, the key steps being the construction of the C(7)-quaternary centre by cyclization of a thionium ion upon the indole 3-position and the introduction of the C(16)-methoxycarbonyl substituent by photochemical rearrangement of the N-methoxycarbonylenamine 7.

  已经从四环中间体1中实现了消旋性 tubotaiwine 8 的总合成，其关键步骤是通过在吲哚3位上的环化反应构建C(7)-季铵中心，以及通过N-甲氧基羰基胺7的光化学重排引入C(16)-甲氧基羰基取代基。
• 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.