7-ethyl-2,3-didehydro-20,21-dinor-aspidospermidine-3-carboxylic acid methyl ester | 26251-92-3

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 鸡蛋花型生物碱
• 英文名称: 7-ethyl-2,3-didehydro-20,21-dinor-aspidospermidine-3-carboxylic acid methyl ester
• 英文别名: methyl (1R,12S,14R,19S)-14-ethyl-8,16-diazapentacyclo[10.6.1.01,9.02,7.016,19]nonadeca-2,4,6,9-tetraene-10-carboxylate
• CAS: 26251-92-3
• 化学式: C₂₁H₂₆N₂O₂
• 分子量: 338.45
• InChiKey: HVESDSXDWBFBHK-PKOZFGMGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.57
• 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：

  (2R,3aS,10bR,12bS)-2-Ethyl-1-thioxo-2,3,3a,4,6,11,12,12b-octahydro-1H-6,12a-diaza-indeno[7,1-cd]fluorene-5-carboxylic acid methyl ester 在 镍 作用下， 以 乙醇 为溶剂， 反应 6.0h， 以78%的产率得到7-ethyl-2,3-didehydro-20,21-dinor-aspidospermidine-3-carboxylic acid methyl ester
  参考文献：
  名称：

  Application of Ferrocenylalkyl Chiral Auxiliaries to Syntheses of Indolenine Alkaloids:  Enantioselective Syntheses of Vincadifformine, ψ- and 20-epi-ψ-Vincadifformines, Tabersonine, Ibophyllidine, and Mossambine

  摘要：

  Condensations of the chiral N-ferrocenylethylindoloazepines 4a,b, with the aldehydes 5, 13, 19, 29, and 32, led to tetracyclic vinylogous urethanes 6a,b and 7,14a and 14b,21a,c and 21b,d,30a and 31a, and 30b and 31b. Respectively, 6:1, 5:1, 3:1, 1.7:1, and 2:1 diastereomeric selections provided intermediates which, on cleavage of the chiral auxiliary N-substituent and subsequent elaboration of ring D of the Aspidosperma and Strychnos alkaloids, provided enantiomerically pure (-)-psi- and (-)-epi-psi-vincadifformines (1, 2), (+)-ibophyllidine (12), (+)-and (-)-vincadifformine (16a, 16b), (-)-tabersonine (27), and (-)-mossambine (41).

  DOI：

  10.1021/jo971838g

文献信息

• Synthesis of (−)-Pseudotabersonine, (−)-Pseudovincadifformine, and (+)-Coronaridine Enabled by Photoredox Catalysis in Flow
  作者：Joel W. Beatty、Corey R. J. Stephenson

  DOI：10.1021/ja506170g

  日期：2014.7.23

  Natural product modification with photo-redox catalysis allows for mild, chemoselective access to a wide array of related structures in complex areas of chemical space, providing the possibility for novel structural motifs as well as useful quantities of less abundant congeners. While amine additives have been used extensively as stoichiometric electron donors for photocatalysis, the controlled modification of amine substrates through single-electron oxidation is ideal for the synthesis and modification of alkaloids. Here, we report the conversion of the amine (+)-catharanthine into the natural products (-)-pseudotabersonine, (-)-pseudovincadifformine, and (+)-coronaridine utilizing visible light photoredox catalysis.