2-(4-fluorophenyl)-1,2,3,4-tetrahydroquinoline | 1402568-43-7

• 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: 2-(4-fluorophenyl)-1,2,3,4-tetrahydroquinoline
• CAS: 1402568-43-7
• 化学式: C₁₅H₁₄FN
• 分子量: 227.281
• InChiKey: BMILSASPAVFJPX-UHFFFAOYSA-N

物化性质

• 沸点：
  368.1±41.0 °C(Predicted)
• 密度：
  1.132±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(4-fluorophenyl)-1,2,3,4-tetrahydroquinoline 在 盐酸 、 (S)-3,3'-bis(2,4,6-tri-iso-propylphenyl)-1,1'-binaphthyl-2,2'-diyl hydrogenphosphate 、 bis(2,6-dichlorobenzyl)-2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate 、 N-(2,2,6,6-tetramethyl-1-oxopiperidin-1-ium-4-yl)acetamide tetrafluoroborate 作用下， 以 正己烷 、 水 、 甲苯 为溶剂， 反应 60.0h， 以87%的产率得到(R)-2-(4-fluorophenyl)-1,2,3,4-tetrahydroquinoline
  参考文献：
  名称：

  Single-Operation Deracemization of 3H-Indolines and Tetrahydroquinolines Enabled by Phase Separation

  摘要：

  The single-operation deracemization of 3H indolines and tetrahydroquinolines is described. An asymmetric redox approach was employed, in which a phosphoric acid catalyst, oxidant, and reductant are present in the reaction mixture. The simultaneous presence of both oxidant and reductant was enabled by phase separation and resulted in the isolation of highly enantioenriched starting materials in high yields.

  DOI：

  10.1021/ja4082827
• 作为产物：
  描述：

  2-氯喹啉 在 四(三苯基膦)钯 、 sodium cyanoborohydride 、 sodium carbonate 、 溶剂黄146 作用下， 以 1,4-二氧六环 、 水 为溶剂， 生成 2-(4-fluorophenyl)-1,2,3,4-tetrahydroquinoline
  参考文献：
  名称：

  Single-Operation Deracemization of 3H-Indolines and Tetrahydroquinolines Enabled by Phase Separation

  摘要：

  The single-operation deracemization of 3H indolines and tetrahydroquinolines is described. An asymmetric redox approach was employed, in which a phosphoric acid catalyst, oxidant, and reductant are present in the reaction mixture. The simultaneous presence of both oxidant and reductant was enabled by phase separation and resulted in the isolation of highly enantioenriched starting materials in high yields.

  DOI：

  10.1021/ja4082827

文献信息

• A General Method for N-Methylation of Amines and Nitro Compounds with Dimethylsulfoxide
  作者：Xue Jiang、Chao Wang、Yawen Wei、Dong Xue、Zhaotie Liu、Jianliang Xiao

  DOI：10.1002/chem.201303802

  日期：2014.1.3

  DMSO methylates a broad range of amines in the presence of formic acid, providing a novel, green and practical method for amine methylation. The protocol also allows the one‐pot transformation of aromatic nitro compounds into dimethylated amines in the presence of a simple iron catalyst.

  DMSO在甲酸存在下将多种胺甲基化，为胺甲基化提供了一种新颖，绿色且实用的方法。该协议还允许在简单的铁催化剂存在下将芳香族硝基化合物单锅转化为二甲基化胺。
• The Remarkable Effect of a Simple Ion: Iodide-Promoted Transfer Hydrogenation of Heteroaromatics
  作者：Jianjun Wu、Chao Wang、Weijun Tang、Alan Pettman、Jianliang Xiao

  DOI：10.1002/chem.201201517

  日期：2012.7.27

  I can do it! Accelerated by simple iodide ions, rhodium‐catalysed transfer hydrogenation can be readily performed on quinolines, isoquinolines and quinoxalines, affording the tetrahydro products in high yields with low catalyst loading (see scheme).

  我能做到！通过简单的碘离子加速，铑催化的转移加氢反应可轻松地在喹啉，异喹啉和喹喔啉上进行，从而以高收率和低催化剂负载量提供四氢产物（参见方案）。
• Iridium‐Catalyzed Hydrogenation and Dehydrogenation of N‐Heterocycles in Water under Mild Conditions
  作者：Shengdong Wang、Haiyun Huang、Christian Bruneau、Cédric Fischmeister

  DOI：10.1002/cssc.201900626

  日期：——

  An efficient catalytic method is presented for the hydrogenation of N‐heterocycles. The iridium‐based catalyst operates under mild conditions in water without any co‐catalyst or stoichiometric additives. The catalyst also promotes the reverse reaction of dehydrogenation of N‐heterocycles, hence displaying appropriate characteristics for a future hydrogen economy based on liquid organic hydrogen carriers

  提出了一种用于N-杂环加氢的有效催化方法。铱基催化剂可在温和的条件下于水中运行，无需任何助催化剂或化学计量的添加剂。催化剂还促进N-杂环脱氢的逆反应，因此基于液态有机氢载体（LOHC）显示出适合未来氢经济的适当特性
• Cu-catalyzed reduction of azaarenes and nitroaromatics with diboronic acid as reductant
  作者：Danwei Pi、Haifeng Zhou、Yanmei Zhou、Qixing Liu、Renke He、Guanshuo Shen、Yasuhiro Uozumi

  DOI：10.1016/j.tet.2018.03.014

  日期：2018.4

  copper-catalyzed reduction of azaarenes with diboronic acid as reductant in an aprotic solvent under mild conditions has been developed. Most interestingly, the nitroazaarenes could be reduced exclusively to give the corresponding amines without touching the azaarene moieties. Furthermore, the reductive amination of aromatic nitro compounds and aromatic aldehydes has also been realized. A series of

  已经开发了在温和条件下在质子惰性溶剂中用二硼酸作为还原剂的无配体铜催化的氮杂芳烃还原方法。最有趣的是，可以将硝基氮杂氮烯只还原成相应的胺而不接触氮杂芳烃部分。此外，还已经实现了芳族硝基化合物和芳族醛的还原胺化。获得了具有良好官能团耐受性的一系列氢化的氮杂芳烃和仲胺。
• Synthesis and kinetic resolution of substituted tetrahydroquinolines by lithiation then electrophilic quench
  作者：Nicholas Carter、Xiabing Li、Lewis Reavey、Anthony J. H. M. Meijer、Iain Coldham

  DOI：10.1039/c7sc04435f

  日期：——

  THF at −78 °C resulted in efficient lithiation at the 2-position and the organolithiums were trapped with a variety of electrophiles to give substituted products. Variable temperature NMR spectroscopy gave kinetic data that showed that the rate of tert-butoxycarbonyl (Boc) rotation was fast (ΔG‡ ≈ 45 kJ mol−1 at −78 °C) and in situ ReactIR spectroscopy showed fast lithiation at −78 °C. By carrying

  在-78°C下，在THF中用正丁基锂处理N -Boc-2-芳基-1,2,3,4-四氢喹啉，导致2位上的有效锂化，并且有机锂被多种亲电试剂捕获给出替代产品。变温核磁共振光谱给出的动力学数据表明叔丁氧羰基 (Boc) 旋转速率很快（-78 °C 时Δ G ‡ ≈ 45 kJ mol -1 ），原位ReactIR 光谱显示在 -78 °C 时快速锂化C.通过在手性配体金雀花碱存在下进行锂化，实现了具有非常高水平的对映选择性的动力学拆分。将所得对映体富集的N -Boc-2-芳基四氢喹啉转化为2,2-二取代产物，对映体纯度没有显着损失。大多数亲电子试剂在 2 位上添加，化学反应提供了一种获得氮原子 α 完全取代的四氢喹啉的方法。值得注意的是，2,2-二取代的四氢喹啉的任一对映体都可以由手性配体的相同对映体以高选择性获得。不同寻常的是，当使用氰基甲酸甲酯作为亲电子试剂时，取代发生在C-2 处连接的芳环的邻位。通过氘同位素研究和