6-(difluoromethyl)-8-methoxyphenanthridine | 1610501-06-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: 6-(difluoromethyl)-8-methoxyphenanthridine
• CAS: 1610501-06-8
• 化学式: C₁₅H₁₁F₂NO
• 分子量: 259.255
• InChiKey: GKARUQJPKOTPDX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.33
• 重原子数：
  19.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  22.12
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  ethyl 2,2-difluoro-2-(8-methoxyphenanthridin-6-yl)acetate 在 potassium carbonate 、 盐酸 作用下， 以 甲醇 、 水 为溶剂， 以91%的产率得到6-(difluoromethyl)-8-methoxyphenanthridine
  参考文献：
  名称：

  Visible-Light-Mediated Fluoroalkylation of Isocyanides with Ethyl Bromofluoroacetates: Unified Synthesis of Mono- and Difluoromethylated Phenanthridine Derivatives

  摘要：

  A practical and unified strategy has been described for the preparation of mono- and difluoromethylated phenanthridine derivatives using a visible-light-promoted alkylation and decarboxylation sequence from biphenyl isocyanides with ethyl bromofluoroacetate (EBFA) or ethyl bromodifluoroacetate (EBDFA). These reactions could be carried out at room temperature in good to excellent chemical yields. Both stepwise and one-pot procedures have been developed, which makes this strategy more attractive.

  DOI：

  10.1021/ol501081h

文献信息

• Radical Fluoroalkylation of Isocyanides with Fluorinated Sulfones by Visible-Light Photoredox Catalysis
  作者：Jian Rong、Ling Deng、Ping Tan、Chuanfa Ni、Yucheng Gu、Jinbo Hu

  DOI：10.1002/anie.201510533

  日期：2016.2.18

  visible‐light photoredox catalysis. A wide range of readily available mono‐, di‐, and trifluoromethyl heteroaryl sulfones can thus be used as efficient radical fluoroalkylation reagents under mild conditions. This method not only describes a new synthetic application of fluorinated sulfones, but also provides a new route to fluoroalkyl radicals.

  可见光光氧化还原催化作用使异氰酸酯与氟化砜发生自由基氟烷基化。因此，在温和的条件下，可以使用各种容易获得的单，二和三氟甲基杂芳基砜作为有效的自由基氟代烷基化试剂。该方法不仅描述了氟化砜的新合成应用，而且为氟代烷基自由基的制备提供了新途径。
• Visible-Light-Driven Difluoromethylation of Isocyanides with <i>S</i>-(Difluoromethyl)diarylsulfonium Salt: Access to a Wide Variety of Difluoromethylated Phenanthridines and Isoquinolines
  作者：Wen-Bing Qin、Wei Xiong、Xin Li、Jia-Yi Chen、Li-Ting Lin、Henry N. C. Wong、Guo-Kai Liu

  DOI：10.1021/acs.joc.0c00816

  日期：2020.8.21

  variety of difluoromethylated phenanthridines and isoquinolines is herein described. Electrophilic S-(difluoromethyl)diarylsulfonium salt proved to be a good difluoromethyl radical precursor under photoredox catalysis. A broad range of isocyanides were tolerated to furnish the corresponding difluoromethylated phenanthridines, isoquinolines, furo[3,2-c]pyridine, and pyrido[3,4-b]indole in moderate to

  本文描述了一种有效的方法，将可见光驱动的异氰酸酯基自由基二氟甲基化处理，以使用各种二氟甲基化菲啶和异喹啉。在光氧化还原催化下，亲电S-（二氟甲基）二芳基ulf盐被证明是良好的二氟甲基自由基前体。在温和的条件下，宽范围的异氰化物可以中等至极好的收率提供相应的二氟甲基化菲啶，异喹啉，呋喃[3,2- c ]吡啶和吡啶并[3,4- b ]吲哚。还提出了一个合理的机制。
• Difluoromethylborates and Muonium for the Study of Isonitrile Insertion Affording Phenanthridines via Imidoyl Radicals
  作者：Kakeru Konagaya、Yu-En Huang、Kazuki Iwami、Tetsuya Fujino、Rikutaro Abe、Reuben Parchment-Morrison、Kenji M. Kojima、Iain McKenzie、Shigekazu Ito

  DOI：10.1021/acs.joc.3c00056

  日期：2023.7.7

  as a source of difluoromethyl radicals for isonitrile insertion, leading to 6-(difluoromethyl)phenanthridines. Tuning the aryl substituents in the difluoromethylborates and oxidizing reagents enabled the synthesis of 6-(difluoromethyl)phenanthridines through the generation of difluoromethyl radical and spontaneous intramolecular cyclization of the CF2H-imidoyl radical intermediates. The presence of

  6-(二氟甲基)菲啶单元是一种在药物和农业化学研究中极具吸引力的氟烷基取代的平面氮杂环。在本文中，我们报道二氟甲基硼酸盐可用作异腈插入的二氟甲基自由基的来源，从而产生 6-(二氟甲基)菲啶。通过调整二氟甲基硼酸盐和氧化剂中的芳基取代基，可以通过生成二氟甲基自由基和CF 2 自发分子内环化来合成6-(二氟甲基)菲啶H-亚氨基自由基中间体。实验证实了二氟甲基自由基的存在，并从理论上支持了亚氨基自由基和快速环化反应等反应机理。此外，我们通过对2-异氰基-4′-甲氧基-1,1′-联苯进行横向场μ子自旋旋转（TF-μSR）测量并使用密度泛函理论（DFT）计算，获得了有关亚氨基自由基中间体的有价值的信息来解释光谱。锷是一种简单的自由基，优先加成到异腈单元的碳原子上，产生相应的亚氨基。
• Radical Difluoromethylation of Thiols with (Difluoromethyl)triphenylphosphonium Bromide
  作者：Niklas B. Heine、Armido Studer

  DOI：10.1021/acs.orglett.7b02109

  日期：2017.8.4

  A method for facile difluoromethylation of various thiols using (difluoromethyl)triphenylphosphonium bromide under mild reaction conditions is presented. The transformation proceeds in the absence of any transition metal using a bench-stable and readily accessible phosphonium salt. Deuterium labeling experiments and cyclic voltammetry measurements reveal that the difluoromethylation occurs via a S(RN)1-type mechanism. Substrate scope is broad, and various functional groups are tolerated (OH, NH2, amide, ester).