4-fluorobenzenediazonium tetrafluoroborate | 459-45-0

• 英文名称: 4-fluorobenzenediazonium tetrafluoroborate
• 英文别名: 4-fluorophenyldiazonium tetrafluoroborate；p-fluorophenyldiazonium tetrafluoroborate；p-fluorobenzenediazonium tetrafluoroborate；p-fluorophenyldiazonium tetrafluoroborate salt
• CAS: 459-45-0
• 化学式: BF₄*C₆H₄FN₂
• 分子量: 209.914
• InChiKey: GCRHTEJQELIWGE-UHFFFAOYSA-N

物化性质

• 溶解度：
  可溶于水

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  4-fluorobenzenediazonium tetrafluoroborate 在 palladium diacetate 甲醇 、 氢氧化钾 、 dimethyl sulfide borane 、 sodium methylate 、 sodium hydride 、 magnesium 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 212.75h， 生成 帕罗西汀杂质04(单体)
  参考文献：
  名称：

  Efficient Heck Arylations of Cyclic and Acyclic Acrylate Derivatives Using Arenediazonium Tetrafluoroborates. A New Synthesis of the Antidepressant Drug (±)-Paroxetine

  摘要：

  The Heck arylation of acyclic- and cyclic-substituted acrylates using several arenediazonium tetrafluoroborates was investigated. Arylations were carried out under aerobic, ligand-free conditions to provide the corresponding substituted acrylates in moderate to high isolated yields. Heck arylations were usually completed in less than 2 h in refluxing methanol. The aza-endocyclic acrylate derivative 11a was converted into the antidepressant drug ((+)(-))-paroxetine in a concise new route in good overall yield.

  DOI：

  10.1021/ol060248e
• 作为产物：
  描述：

  在 亚硝酸特丁酯 作用下， 以 四氢呋喃 为溶剂， 生成 4-fluorobenzenediazonium tetrafluoroborate
  参考文献：
  名称：

  Discovery and structure-activity relationship studies of 1-aryl-1H-naphtho[2,3-d][1,2,3]triazole-4,9-dione derivatives as potent dual inhibitors of indoleamine 2,3-dioxygenase 1 (IDO1) and trytophan 2,3-dioxygenase (TDO)

  摘要：

  Indoleamine 2,3-dioxygenase 1 (IDO1) and tryptophan 2,3-dioxygenase (TDO), which mediate kynurenine pathway of tryptophan degradation, have emerged as potential new targets in immunotherapy for treatment of cancer because of their critical role in immunosuppression in the tumor microenvironment. In this investigation, we report the structural optimization and structure-activity relationship studies of 1-phenyl-1H-naphtho[2,3-d][1,2,3]triazole-4,9-dione derivatives as a new class of IDO1/TDO dual inhibitors. Among all the obtained dual inhibitors, 1-(3-chloro-4-fluorophenyl)-6-fluoro-1H-naphtho[2,3-d][1,2,3]triazole-4,9-dione (38) displayed the most potent IDO1 and TDO inhibitory activities with IC₅₀ (half-maximal inhibitory concentration) values of 5 nM for IDO1 and 4 nM for TDO. It turned out that compound 38 was not a PAINS compound. Compound 38 could efficiently inhibit the biofunction of IDO1 and TDO in intact cells. In LL2 (Lewis lung cancer) and Hepa1-6 (hepatic carcinoma) allograft mouse models, this compound also showed considerable in vivo anti-tumor activity and no obvious toxicity was observed. Therefore, 38 could be a good lead compound for cancer immunotherapy and deserving further investigation.

  DOI：

  10.1016/j.ejmech.2020.112703
• 作为试剂：
  描述：

  2-乙烯基萘 、 联硼酸频那醇酯 在 tris-(dibenzylideneacetone)dipalladium(0) 、 4-fluorobenzenediazonium tetrafluoroborate 、 caesium carbonate 作用下， 以 戊醇 为溶剂， 反应 12.0h， 以12 mg的产率得到4,4,5,5-tetramethyl-2-(1-(naphthalen-2-yl)ethyl)-1,3,2-dioxaborolane
  参考文献：
  名称：

  钯催化乙烯基芳烃的区域选择性芳基化

  摘要：

  已经公开了钯芳烃与四氟硼酸芳基重氮和双（频哪醇）二硼的钯催化的1，2-芳基硼化。首次报道苯乙烯衍生物可以成功地用作烯烃的1,2-芳基硼化的良好底物。机理研究表明，在我们的标准条件下，没有发生Pd-H的重新插入，这是该转化成功的关键。

  DOI：

  10.1021/acs.orglett.6b02527

文献信息

• Room-Temperature C–H Arylation: Merger of Pd-Catalyzed C–H Functionalization and Visible-Light Photocatalysis
  作者：Dipannita Kalyani、Kate B. McMurtrey、Sharon R. Neufeldt、Melanie S. Sanford

  DOI：10.1021/ja208068w

  日期：2011.11.23

  This communication describes the development of a room-temperature ligand-directed C-H arylation reaction using aryldiazonium salts. This was achieved by the successful merger of palladium-catalyzed C-H functionalization and visible-light photoredox catalysis. The new method is general for a variety of directing groups and tolerates many common functional groups.

  该通讯描述了使用芳基重氮盐进行室温配体导向的 CH 芳基化反应的开发。这是通过钯催化的 CH 官能化和可见光光氧化还原催化的成功合并实现的。新方法适用于各种导向基团，并能容忍许多常见的官能团。
• A Selective and Benign Synthesis of Functionalized Benzalacetones <i>via</i> Mizoroki–Heck Reaction Using Aryldiazonium Salts
  作者：Therese Stern、Sven Rückbrod、Constantin Czekelius、Constanze Donner、Heiko Brunner

  DOI：10.1002/adsc.200900868

  日期：2010.10.9

  Palladium-catalyzed Mizoroki–Heck reactions were carried out in the presence of calcium carbonate in alcoholic solvents. Under these conditions an efficient preparation of functionalized benzalacetones was developed. The reactions were carried out at room temperature and aerobic conditions, giving the products within several minutes in up to 95% isolated yields. Furthermore, some kinetic investigations

  钯催化的Mizoroki-Heck反应是在碳酸钙存在下于醇类溶剂中进行的。在这些条件下，开发了一种高效制备功能化苯并丙酮的方法。反应在室温和有氧条件下进行，数分钟内获得产物，分离产率高达95％。此外，还介绍了一些动力学研究，机理见解和注意事项。
• [3 + 2] Cycloaddition of Isocyanides with Aryl Diazonium Salts: Catalyst-Dependent Regioselective Synthesis of 1,3- and 1,5-Disubstituted 1,2,4-Triazoles
  作者：Jian-Quan Liu、Xuanyu Shen、Yihan Wang、Xiang-Shan Wang、Xihe Bi

  DOI：10.1021/acs.orglett.8b03069

  日期：2018.11.2

  An unprecedented catalyst-dependent regioselective [3 + 2] cycloaddition of isocyanides with aryl diazonium salts is reported. 1,3-Disubstituted 1,2,4-triazoles were selectively obtained in high yield under Ag(I) catalysis, whereas 1,5-disubstituted 1,2,4-triazoles were formed by Cu(II) catalysis. These catalytic methodologies provide a controlled, modular, and facile access to 1,2,4-triazole scaffolds

  据报道，前所未有的催化剂依赖性异氰酸酯与芳基重氮盐的区域选择性[3 + 2]环加成反应。在Ag（I）催化下，高收率选择性地获得了1,3-二取代的1,2,4-三唑，而在Cu（II）催化下形成了1,5-二取代的1,2,4-三唑。这些催化方法学提供了高效，宽泛的底物范围和出色的官能团相容性的1,2,4-三唑支架的受控，模块化和便捷操作。
• A general electrochemical strategy for the Sandmeyer reaction
  作者：Qianyi Liu、Beiqi Sun、Zheng Liu、Yi Kao、Bo-Wei Dong、Shang-Da Jiang、Feng Li、Guoquan Liu、Yang Yang、Fanyang Mo

  DOI：10.1039/c8sc03346c

  日期：——

  Herein we report a general electrochemical strategy for the Sandmeyer reaction. Using electricity as the driving force, this protocol employs a simple and inexpensive halogen source, such as NBS, CBrCl3, CH2I2, CCl4, LiCl and NaBr for the halogenation of aryl diazonium salts. In addition, we found that these electrochemical reactions could be performed using anilines as the starting material in a one-pot

  本文中，我们报告了桑德迈尔反应的一般电化学策略。使用电作为驱动力，该协议采用一种简单且廉价的卤素源，例如NBS，CBrCl 3，CH 2 I 2，CCl 4，LiCl和NaBr进行芳基重氮盐的卤化。另外，我们发现这些电化学反应可以以一锅的方式使用苯胺作为起始原料来进行。此外，该方法的实用性在使用非常便宜的石墨作为电极的多克规模的芳基卤化物的合成中得到了证明。已经进行了一系列详细的机理研究，包括自由基时钟和自由基清除剂研究，循环伏安分析和原位电子顺磁共振（EPR）分析。
• Sandmeyer reactions. Part 7.1 An investigation into the reduction steps of Sandmeyer hydroxylation and chlorination reactions
  作者：Peter Hanson、Jason R. Jones、Alec B. Taylor、Paul H. Walton、Allan W. Timms

  DOI：10.1039/b200748g

  日期：2002.5.22

  aqueous solution, the reduction steps have been investigated by means of correlation analyses of the effects of diazonium ion substitution on the rates of reduction. For simple hydroxylation, a change of behaviour between diazonium ions substituted by electron donor groups and those substituted by electron acceptor groups is interpreted as a change within an inner-sphere process from rate-determining electron

  对于桑德迈尔水溶液中的羟基化和氯化反应，通过相关分析重氮离子取代对还原速率的影响，研究了还原步骤。对于简单的羟基化，被电子给体基团取代的重氮离子与被电子受体基团取代的重氮离子之间的行为变化被解释为内球过程中从速率确定电子转移到反应物速率确定缔合的变化。相比之下，对于柠檬酸盐促进的羟基化，类似的行为变化可解释为内层和外层电子转移之间的变化。对于氯化作用，在所检查的取代基范围内没有机理上的变化，但其行为方式与内球机理一致。根据重氮离子取代和催化剂连接对各种反应性氧化还原对的还原电势和自交换速率的影响，合理化了各种行为方式。重氮离子的还原反应和其他亲电反应的比较相关性分析用于支持关于Sandmeyer还原步骤的高级论证。建议铜我还原剂反应经由亲核桥连配体的重氮Ñ β以得到瞬变ž-adducts其为前体配合物和活化用于电子转移包括关于N-N键的旋转。