2,3,6,7-Tetramethoxy-9,10,11,12,12a,13-hexahydro-9a-aza-cyclopenta[b]triphenylene | 25908-92-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: 2,3,6,7-Tetramethoxy-9,10,11,12,12a,13-hexahydro-9a-aza-cyclopenta[b]triphenylene
• 英文别名: tylophorine；Tylophorin；(±)-tylophorine；rac-tylophorine；2,3,6,7-tetramethoxy-9,11,12,13,13 a,14-hexahydrodibenzo[f,h]pyrrolo[1,2-b]isoquinoline；2,3,6,7-tetramethoxy-9,11,12,13,13a,14-hexahydrophenanthro[9,10-f]indolizine
• CAS: 25908-92-3
• 化学式: C₂₄H₂₇NO₄
• 分子量: 393.483
• InChiKey: SSEUDFYBEOIWGF-UHFFFAOYSA-N

物化性质

• 熔点：
  287 °C (decomp)
• 沸点：
  559.9±45.0 °C(Predicted)
• 密度：
  1.26±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  40.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2,3,6,7-Tetramethoxy-9,10,11,12,12a,13-hexahydro-9a-aza-cyclopenta[b]triphenylene 在 氢碘酸 作用下， 以 甲醇 、 氯仿 为溶剂， 反应 2.0h， 生成 tylophorine hydroiodide
  参考文献：
  名称：

  Synthesis and Antiviral Activities of Phenanthroindolizidine Alkaloids and Their Derivatives

  摘要：

  Racemic phenanthroindolizidine alkaloids tylophorine, antofine, and deoxytylophorinine, and optically pure alkaloids S-(+)-tylophorine and R-(-)-tylophorine were synthesized and evaluated for their antiviral activities against tobacco mosaic virus (TMV). Further salinization modifications based on tylophorine increased stability and water solubility and improved the antiviral activity in application. The bioassay results showed that most of these synthesized compounds showed higher antiviral activity against TMV in vitro and in vivo than commercial Ningnanmycin. Especially, tylophorine salt derivatives 10, 11, 13, 17, and 22 emerged as potential inhibitors of plant virus. These findings demonstrate that these phenanthroindolizidine alkaloids and their salt derivatives represent a new template for antiviral studies and could be considered for novel therapy against plant virus infection.

  DOI：

  10.1021/jf902543r
• 作为产物：
  描述：

  1-溴-2-碘-4,5-二甲氧基苯 在 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride 、 三氟代氧化钒(V) 、 叔丁基锂 、 sodium carbonate 、 三氟乙酸 、 三氟乙酸酐 、 lithium chloride 作用下， 以 四氢呋喃 、 乙二醇二甲醚 、 二氯甲烷 、 水 、 乙酸乙酯 为溶剂， 反应 20.5h， 生成 2,3,6,7-Tetramethoxy-9,10,11,12,12a,13-hexahydro-9a-aza-cyclopenta[b]triphenylene
  参考文献：
  名称：

  Synthesis of Tylocrebrine and Related Phenanthroindolizidines by VOF₃-Mediated Oxidative Aryl-Alkene Coupling

  摘要：

  A highly convergent strategy to prepare phenanthroindolizidines is reported involving three consecutive C-C coupling reactions. This sequence features a novel VOF3-mediated aryl-alkene coupling in the final step, which enables regioselective preparation of C5-substituted phenanthroindolizidines for the first time. This strategy has been applied to the synthesis of eight natural and unnatural members in this class to investigate the scope of this chemistry and to explore structure-activity relationships.

  DOI：

  10.1021/ol1023954

文献信息

• A General Cp*Co^III-Catalyzed Intramolecular C−H Activation Approach for the Efficient Total Syntheses of Aromathecin, Protoberberine, and Tylophora Alkaloids
  作者：Andreas Lerchen、Tobias Knecht、Maximilian Koy、Constantin G. Daniliuc、Frank Glorius

  DOI：10.1002/chem.201702648

  日期：2017.9.7

  Herein, we report a Cp*CoIII‐catalyzed C−H activation approach as the key step to create highly valuable isoquinolones and pyridones as building blocks that can readily be applied in the total syntheses of a variety of aromathecin, protoberberine, and tylophora alkaloids. This particular C−H activation/annulation reaction was achieved with several terminal as well as internal alkyne coupling partners

  在此，我们报告Cp * Co III催化的C H活化方法是创建高度有价值的异喹诺酮和吡啶酮的重要步骤，这些异喹啉酮和吡啶酮可以轻松地用于各种芳香族素，原小ber碱和tylophora生物碱的总合成。这种特殊的CH活化/环化反应是通过多个末端以及内部炔烃偶联伙伴实现的，具有广泛的应用范围和出色的官能团耐受性。本文报道的该方案的合成适用性已在两个Topo-I-抑制剂和两个8-氧代小ber碱核心的合成中得到了证明，这些核心可进一步制成四氢小ber碱和原小ber碱生物碱。此外，这些构件也以方便的方式转化为六种不同的tylophora生物碱。
• Total Synthesis of Phenanthropiperidine Alkaloids by Sequential Alkylation of <i>N</i> , <i>N</i> ‐Dibenzylaminoacetonitrile
  作者：Christelle Bouvry、Milène Franzetti、Jean‐François Cupif、Jean‐Pierre Hurvois

  DOI：10.1002/ejoc.202101131

  日期：2021.11.25

  Tylophorine and cryptopleurine were synthesized by condensation of metallated α-aminonitriles with bromomethylphenanthrenes to provide fully substituted α-aminonitriles, which are subjected to a reductive decyanation to form homobenzylic amines. From these intermediates, the E- and D-rings of tylophorine and cryptopleurine were formed through the displacement of a terminal leaving group and by a late

  Tylophorine 和 cryptopleurine 是通过金属化的 α-氨基腈与溴甲基菲缩合得到完全取代的 α-氨基腈合成的，然后进行还原脱氰以形成高苄胺。从这些中间体中，分别通过末端离去基团的置换和晚期 Pictet-Spengler 缩合形成 tylophorine 和 cryptopleurine 的 E 和 D 环。
• A general approach to triphenylenes and azatriphenylenes: total synthesis of dehydrotylophorine and tylophorine
  作者：Andrew McIver、Douglas D. Young、Alexander Deiters

  DOI：10.1039/b811068a

  日期：——

  A convergent and flexible synthesis of substituted triphenylenes, azatriphenylenes, and the cytotoxic alkaloids dehydrotylophorine and tylophorine has been developed.

  已经开发了一种聚合的，灵活的取代三苯，氮杂三苯以及细胞毒性生物碱脱氢酪氨酸和酪氨酸的合成方法。
• Synthesis of tylophorine
  作者：V.K. Mangla、D.S. Bhakuni

  DOI：10.1016/0040-4020(80)80227-4

  日期：1980.1

  A biogenetic type of synthesis of tylorphorine 12 (3.8% yield, established by a radio-dilution method) was achieved by ferricyanide oxidation of 6,7-di(3-hydroxy-4-methoxyphenyl)-6,7-dehydroindolizidine 10.

  甲生物遗传型tylorphorine的合成的12（3.8％产率，由无线电稀释法建立）是由6,7-二（3-羟基-4-甲氧基苯基）铁氰化物氧化实现-6,7- dehydroindolizidine 10。
• Synthesis of (±)-septicine and (±)-tylophorine by regioselective [3 + 2] cycloaddition
  作者：Hideo Iida、Masao Tanaka、Chihiro Kibayashi

  DOI：10.1039/c39830000271

  日期：——

  The synthesis of (±)-septicine and (±)-tylophorine, using 1,3-dipolar cycloaddition and intramolecular photocyclisation reactions as key steps, is described.

  描述了使用1，3-偶极环加成和分子内光环化反应作为关键步骤的（±）-败血碱和（±）-酪氨酸的合成。

表征谱图