(+/-)-pseudotabersonine | 21218-00-8

• 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: (+/-)-pseudotabersonine
• 英文别名: Ψ-tabersonine；pseudotaberosine；Pseudotabersonine；methyl (1S,12S,19R)-14-ethyl-8,16-diazapentacyclo[10.6.1.01,9.02,7.016,19]nonadeca-2,4,6,9,13-pentaene-10-carboxylate
• CAS: 21218-00-8；35478-76-3；54244-12-1
• 化学式: C₂₁H₂₄N₂O₂
• 分子量: 336.434
• InChiKey: QBRYFKNKDKXNFZ-YFZFPPMRSA-N

物化性质

• 沸点：
  498.8±45.0 °C(Predicted)
• 密度：
  1.27±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  25
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  41.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (+/-)-pseudotabersonine 在 palladium on activated charcoal 氢气 作用下， 以 乙酸乙酯 为溶剂， 反应 5.0h， 以93%的产率得到(+/-)-20-epi-pseudovincadifformine
  参考文献：
  名称：

  A common intermediate providing syntheses of .PSI.-tabersonine, coronaridine, iboxyphylline, ibophyllidine, vinamidine, and vinblastine

  摘要：

  Generation of the key tetracyclic intermediates 14a,b in six steps (42% overall) and subsequent short reduction, oxidation, and arylation sequences results in total syntheses of the title compounds 8, 9, 10, 11, 12, and 13.

  DOI：

  10.1021/jo00032a029
• 作为产物：
  描述：

  2-已烯醛 在 盐酸 、 4,4'-di(tert-butyl)-[1,1-biphenyl]yllithium 、 三氟化硼乙醚 、 potassium tert-butylate 、 四丁基碘化铵 、 potassium diisopropylamide 、 对甲苯磺酸 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 52.0h， 生成 (+/-)-pseudotabersonine
  参考文献：
  名称：

  Biomimetic total synthesis of pseudotabersonine: a novel oxindole-based approach to construction of Aspidosperma alkaloids

  摘要：

  DOI：

  10.1021/ja00056a059

文献信息

• Concise Total Synthesis of (±)-Pseudotabersonine via Double Ring-Closing Metathesis Strategy
  作者：Bo Cheng、James D. Sunderhaus、Stephen F. Martin

  DOI：10.1021/ol101356u

  日期：2010.8.20

  A concise synthesis of (±)-pseudotabersonine from commercially available 1-(phenylsulfonyl)-3-indolecarboxaldehyde has been accomplished. This synthesis features the convergent assembly of a key intermediate via a stepwise variant of a Mannich-type multicomponent coupling process, a double ring-closing metathesis, and a one-pot deprotection/cyclization reaction.

  (±)-pseudotabersonine 从市售 1-(苯磺酰基)-3-indolecarboxaldehyde 的简明合成已经完成。该合成的特点是通过曼尼希型多组分偶联过程的逐步变体、双闭环复分解和一锅脱保护/环化反应来聚合组装关键中间体。
• Applications of ring closing metathesis. Total synthesis of (±)-pseudotabersonine
  作者：Bo Cheng、James D. Sunderhaus、Stephen F. Martin

  DOI：10.1016/j.tet.2015.04.082

  日期：2015.9

  A novel approach to the Aspidosperma family of alkaloids was developed and applied to a concise total synthesis of (±)-pseudotabersonine that was accomplished in 11 steps. Key transformations include a stepwise variant of a Mannich-like multicomponent assembly process, a double ring-closing metathesis sequence, and a one-pot deprotection/cyclization reaction.

  开发了一种新的方法用于曲霉属生物碱类，并将其应用于简明的（±）-假烟碱的全合成中，该合成过程可分11个步骤完成。关键的转化包括曼尼希样多组分组装过程的逐步变体，双闭环复分解序列和一锅脱保护/环化反应。
• Stereodivergent Synthesis of Pseudotabersonine Alkaloids
  作者：Mihail Kazak、Martins Priede、Kirill Shubin、Hannah E. Bartrum、Jean-François Poisson、Edgars Suna

  DOI：10.1021/acs.orglett.7b02635

  日期：2017.10.6

  An eight-step stereodivergent synthesis of enantiomerically pure (−)-14-epi-pseudotabersonine and (+)-pseudotabersonine has been developed from a common N-tert-butanesulfinyl ketimine key intermediate.

  对映体纯的（-）-14-表-伪烟碱和（+）-伪烟碱的八步立体发散合成已从一种常见的N-叔-丁亚磺酰基酮亚胺关键中间体发展而来。
• Recycling Upstream Redox Enzymes Expands the Regioselectivity of Cycloaddition in Pseudo-Aspidosperma Alkaloid Biosynthesis
  作者：Mohamed O. Kamileen、Matthew D. DeMars、Benke Hong、Yoko Nakamura、Christian Paetz、Benjamin R. Lichman、Prashant D. Sonawane、Lorenzo Caputi、Sarah E. O’Connor

  DOI：10.1021/jacs.2c08107

  日期：2022.11.2

  allows cycloaddition reactions with alternative regioselectivity. By incubating dehydrosecodine with reductase and oxidase biosynthetic enzymes that act upstream in the pathway, we can access the rare pseudoaspidosperma alkaloids pseudo-tabersonine and pseudo-vincadifformine, both in vitro and by reconstitution in the plant Nicotiana benthamiana from an upstream intermediate. We propose a stepwise mechanism

  大自然使用环加成反应来生成复杂的天然产物支架。Dehydrosecodine 是一种高反应性生物合成中间体，它经过环加成反应生成几种生物碱骨架，这些骨架是长春花碱和伊博加因等具有重要药理学意义的化合物的前体。在这里，我们报告了脱氢仲可定如何进行氧化还原化学反应，这反过来又允许进行具有替代区域选择性的环加成反应。通过将脱氢秒可定与作用于该通路上游的还原酶和氧化酶生物合成酶一起孵育，我们可以在体外和通过在植物本塞姆氏烟草中重组获得稀有的拟刺孢植物生物碱伪塔贝松碱和伪长春二福明来自上游中间体。我们提出了一种逐步机制，通过对酶中间体进行结构表征和监测氘标记的掺入来解释伪塔贝松碱支架的形成。这一发现突出了植物如何使用氧化还原酶从常见前体对映选择性地生成新支架。
• 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.