2,3,4',5,6-pentafluoro-1,1'-biphenyl | 505058-33-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,3,4',5,6-pentafluoro-1,1'-biphenyl
• 英文别名: 1,1'-Biphenyl, 2,3,4',5,6-pentafluoro-；1,2,4,5-tetrafluoro-3-(4-fluorophenyl)benzene
• CAS: 505058-33-3
• 化学式: C₁₂H₅F₅
• 分子量: 244.164
• InChiKey: HXZWKJSEHCCJAC-UHFFFAOYSA-N

物化性质

• 沸点：
  237.4±35.0 °C(Predicted)
• 密度：
  1.389±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  、 2,3,4',5,6-pentafluoro-1,1'-biphenyl 在 copper(l) iodide 、 二苯基-2-吡啶膦 、 norbornene 、 palladium diacetate 、 caesium carbonate 作用下， 以 乙腈 为溶剂， 反应 24.0h， 以51%的产率得到5-methoxy-4-(2,3,4',5,6-pentafluoro-[1,1'-biphenyl]-4-yl)-2,3-dihydrobenzofuran
  参考文献：
  名称：

  Synthesis of polyfluoroarene-substituted benzofuran derivatives via cooperative Pd/Cu catalysis

  摘要：

  通过共同作用的Pd/Cu催化剂，开发了电子亏缺的多氟芳烃与芳基卤化物的双C-H键活化。

  DOI：

  10.1039/c8cc00489g
• 作为产物：
  描述：

  1,2,4,5-四氟苯 在 palladium diacetate 正丁基锂 作用下， 以 乙二醇二甲醚 、 乙醚 、 正己烷 为溶剂， 反应 5.0h， 生成 2,3,4',5,6-pentafluoro-1,1'-biphenyl
  参考文献：
  名称：

  The palladium-catalysed cross-coupling reaction of lithium polyfluorophenyltrimethoxyborates with 4-fluoroiodobenzene

  摘要：

  Li[C6F5B(OMe)(3)]. Li[C6HF4B(OMe)(3)] (all three isomers) and Li[3,4,5-C6H2F3B(OMe)(3)] are the first examples of polyfluorophenyltrimethoxyborate salts which have been applied as reagents to Pd-catalysed cross-coupling reactions. A series of polyfluorinated biphenyls C6H5-nFn-C6H4F-4' were obtained from Li[C6H5-nFnB(OMe)(3)] and the model substrate 4-FC6H4I in the presence of Pd catalysts. The influence of the number and the position of fluorine atoms in the polyfluorophenyltrimetboxyborate salts on the reactivity in the coupling reaction was elucidated. (C) 2003 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-1139(03)00088-5

文献信息

• An “On-Cycle” Precatalyst Enables Room-Temperature Polyfluoroarylation Using Sensitive Boronic Acids
  作者：Liye Chen、Haydn Francis、Brad P. Carrow

  DOI：10.1021/acscatal.8b00341

  日期：2018.4.6

  fluorinated arylboronic acid building blocks in cross-coupling has remained challenging, because of their acute base sensitivity. We report a general solution to this problem using a true catalytic intermediate, Pd(PAd3)(p-FC6H4)Br, as a uniquely effective “on-cycle” precatalyst that allows Suzuki–Miyaura coupling to occur much faster than even the most severe protodeboronation side reactions. Control of boron

  交叉偶联中使用氟化芳基硼酸结构单元仍然具有挑战性，因为它们具有敏锐的碱敏感性。我们报告了使用真正的催化中间体Pd（PAd 3）（p -FC 6 H 4）Br作为唯一有效的“循环”预催化剂，可以使Suzuki-Miyaura偶联发生的速度快得多的一般解决方案。即使是最严重的原去硼副反应。还发现控制活性酸形式和休眠酯形式之间的硼形态在平衡催化速率与试剂分解之间起着至关重要的作用。该方法与任何氟化模式，对碱不稳定的官能团以及一系列溴（杂）芳烃均兼容。
• Highly Selective Pd-Catalyzed Direct C–F Bond Arylation of Polyfluoroarenes
  作者：Zhi-Ji Luo、Hai-Yang Zhao、Xingang Zhang

  DOI：10.1021/acs.orglett.8b00692

  日期：2018.5.4

  A directing-group-free palladium-catalyzed direct arylation of simple polyfluoroarenes with arylboronic acids through selective C–F bond activation is described. The combination of Pd(OAc)2 with BrettPhos was identified as an efficient catalytic system to promote the reaction with high regioselectivity and broad substrate scope. Preliminary mechanistic studies reveal that the oxidative addition of

  描述了通过选择性CF键活化，无直接基团的钯催化的简单多氟芳烃与芳基硼酸的直接芳基化。Pd（OAc）2与BrettPhos的结合被认为是一种有效的催化体系，具有高区域选择性和广泛的底物范围，可促进反应。初步的机理研究表明，Pd在C-F键上的氧化加成参与了催化循环。
• Weakly nucleophilic potassium aryltrifluoroborates in palladium-catalyzed Suzuki–Miyaura reactions: relative reactivity of K[4-RC₆F₄BF₃] and the role of silver-assistance in acceleration of transmetallation
  作者：Vadim V Bardin、Anton Yu Shabalin、Nicolay Yu Adonin

  DOI：10.3762/bjoc.11.68

  日期：——

  Small differences in the reactivity of weakly nucleophilic potassium aryltrifluoroborates are revealed in the silver-assisted Pd-catalyzed cross-coupling of K[4-RC₆F₄BF₃] (R = H, Bu, MeO, EtO, PrO, iPrO, BuO, t-BuO, CH₂=CHCH₂O, PhCH₂O, PhCH₂CH₂O, PhO, F, pyrazol-1-yl, pyrrol-1-yl, and indol-1-yl) with ArX (4-BrC₆H₄CH₃, 4-IC₆H₄F and 3-IC₆H₄F). An assumed role of silver(I) compounds Ag_mY (Y = O, NO₃, SO₄, BF₄, F) consists in polarization of the Pd–X bond in neutral complex ArPdL_nX with the generation of the related transition state or formation of [ArPdL_n][XAg_mY] with a highly electrophilic cation and subsequent transmetallation with the weakly nucleophilic borate. Efficiency of Ag_mY as a polarizing agent decreases in order Ag₂O > AgNO₃ ≈ Ag₂SO₄ > Ag[BF₄] > AgF. No clear correlation between the reactivity of K[4-RC₆F₄BF₃] and substituent electron parameters, σ_I and σ_R°, of the aryl group 4-RC₆F₄ was found.

  在银辅助的Pd催化下，揭示了弱亲核性钾芳基三氟硼酸盐在K[4-RC₆F₄BF₃]（R = H，Bu，MeO，EtO，PrO，iPrO，BuO，t-BuO，CH₂=CHCH₂O，PhCH₂O，PhCH₂CH₂O，PhO，F，吡唑-1-基，吡咯-1-基和吲哚-1-基）与ArX（4-BrC₆H₄CH₃，4-IC₆H₄F和3-IC₆H₄F）的交叉偶联中的反应性的细微差异。银(I)化合物Ag_mY（Y = O，NO₃，SO₄，BF₄，F）的假定作用在于极化中性配合物ArPdL_nX中的Pd–X键，生成相关的过渡态或形成[ArPdL_n][XAg_mY]，其中阳离子具有高电子亲合性，随后与弱亲核性硼酸盐进行金属转移。作为极化剂的Ag_mY的效率按顺序降低为Ag₂O > AgNO₃ ≈ Ag₂SO₄ > Ag[BF₄] > AgF。未发现K[4-RC₆F₄BF₃]的反应性与取代基电子参数aryl group 4-RC₆F₄的σ_I和σ_R°之间的明确相关性。
• A new application of (polyfluoroorgano)trifluoroborate salts: the palladium-catalysed cross-coupling reaction with substituted benzenediazonium tetrafluoroborates
  作者：Hermann-Josef Frohn、Nicolay Yu. Adonin、Vadim V. Bardin、Vladimir F. Starichenko

  DOI：10.1016/s0022-1139(02)00157-4

  日期：2002.10

  influence of the number and the position of the fluorine atoms in the (polyfluorophenyl)trifluoroborate salts on the reactivity in the coupling reaction was elucidated. In addition to (polyfluorophenyl)trifluoroborate salts, the cross-coupling was expanded to a first example of a perfluoroalkenyl reagent. K[CF2CFBF3] reacted with [4-FC6H4N2][BF4] and formed CF2CF–C6H4F-4.

  首次（多氟有机）三氟硼酸盐，即K [C 6 F 5 BF 3 ]，K [C 6 HF 4 BF 3 ]（所有三种异构体），K [3,4,5-C 6 H 2 F 3 BF 3 ]和K [CF 2 CFBF 3 ]的主要应用于作为试剂用于钯催化的交叉偶联反应。由K [C 6 H 5– n F n获得了一系列多氟联苯C 6 H 5– n F n –C 6 H 4 X-4'BF 3 ]和底物[4-XC 6 H 4 N 2 ] [BF 4 ]在Pd催化剂的存在下。阐明了（多氟苯基）三氟硼酸盐中氟原子的数目和位置对偶联反应中反应性的影响。除了（聚氟苯基）三氟硼酸盐以外，交叉偶联扩展为全氟烯基试剂的第一个实例。K [CF 2 CFBF 3 ]与[4-FC反应6 ħ 4 Ñ 2 ] [BF 4 ]和形成CF 2 CF-C 6 H ^ 4 F-4。
• Mild and Efficient Ni-Catalyzed Biaryl Synthesis with Polyfluoroaryl Magnesium Species: Verification of the Arrest State, Uncovering the Hidden Competitive Second Transmetalation and Ligand-Accelerated Highly Selective Monoarylation
  作者：Junya Wang、Ge Meng、Kun Xie、Liting Li、Huaming Sun、Zhiyan Huang

  DOI：10.1021/acscatal.7b02618

  日期：2017.11.3

  Employing a nickel catalyst and electron-deficient polyfluoroaryl magnesium species, a highly selective monoarylation of polyfluoroarenes containing multiple identical coupling sites has been achieved for the first time, which represents a long-standing problem due to the competitive reactivity between the desired products and the starting polyfluoroarenes. Because of the negative fluorine effect,

  利用镍催化剂和缺电子的多氟芳基镁物质，首次实现了具有多个相同偶联位点的多氟芳烃的高选择性单芳基化，由于所需产物与起始原料之间的竞争反应性，这是一个长期存在的问题。多氟芳烃。由于负氟效应，分离出了通过X射线晶体学证实的出乎意料的稳定的顺式[Ni（Ar F4）2（DPEPhos）]种类4（Ar F4 = 2,3,5,6-四氟苯基），其作用与通过热分解试验证明催化剂的阻滞状态。进一步的反重金属化实验发现了Ar之间隐藏的二次重金属化F4 -Ni-Ph和过量的Ar F4- MgCl在高价镍中心与所需的但不希望发生的还原性消除竞争。因此，通过新开发的DMM-DPEPhos的协同作用，以及与格氏试剂的二恶烷介导的Schlenk平衡，显着抑制了相应的阻滞状态的形成。因此，一般的亲和力范围和在温和条件下良好的官能团耐受性通常可实现出色的偶联效率和出色的单芳基选择性。重要的是，我们的新方法在噻吩-2,3,5,