2,3,5,6-tetrafluoro-4-methoxy-4'-methylbiphenyl

• 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: 2,3,5,6-tetrafluoro-4-methoxy-4'-methylbiphenyl
• 英文别名: 1,2,4,5-Tetrafluoro-3-methoxy-6-(4-methylphenyl)benzene；1,2,4,5-tetrafluoro-3-methoxy-6-(4-methylphenyl)benzene
• 化学式: C₁₄H₁₀F₄O
• 分子量: 270.226
• InChiKey: AWGKPUDYOYHWNU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  4-碘甲苯 、 2,3,5,6-四氟茴香醚 在 copper(l) iodide 、 四(三苯基膦)钯 、 lithium tert-butoxide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 以80%的产率得到2,3,5,6-tetrafluoro-4-methoxy-4'-methylbiphenyl
  参考文献：
  名称：

  Ligand-free Palladium/Copper Co-catalyzed Direct Arylation of Polyfluoroarenes with Aryl Iodides

  摘要：

  我们开发出了多氟烯烃与芳基碘化物直接芳基化的新反应条件。该反应可由不含配体的钯=铜协同催化，并表现出极佳的官能团兼容性。

  DOI：

  10.5560/znb.2013-3105

文献信息

• Ligand-free Palladium/Copper Co-catalyzed Direct Arylation of Polyfluoroarenes with Aryl Iodides
  作者：Xinyan Zhang、Jian Yu、Guobing Yan

  DOI：10.5560/znb.2013-3105

  日期：2013.8.1

  New reaction conditions for the direct arylation of polyfluoroarenes with aryl iodides have been developed. This reaction can be co-catalyzed by palladium=copper without ligands and exhibits excellent functional group compatibility.

  我们开发出了多氟烯烃与芳基碘化物直接芳基化的新反应条件。该反应可由不含配体的钯=铜协同催化，并表现出极佳的官能团兼容性。
• Direct palladium-catalyzed desulfitative CC coupling of polyfluoroarenes with arylsulfinate salts: Water-accelerated reactions
  作者：Xiaoxi Lin、Yi You、Zhiqiang Weng

  DOI：10.1016/j.jfluchem.2014.06.017

  日期：2014.9

  A new approach to the synthesis of fluorinated biaryl compounds from easily available starting materials is described. This protocol is based on the direct palladium-catalyzed desulfitative cross-coupling of polyfluoroarenes with various arylsulfinate salts via CH bond activation, accelerated by trace amount of water. The method allows the synthesis of various fluorinated biaryl products in moderate

  描述了一种由容易获得的起始原料合成氟化联芳基化合物的新方法。该协议基于直接钯催化desulfitative交叉偶联以通过C芳基亚各种盐polyfluoroarenes的H键活化，通过水的微量加速。该方法允许的各种氟化二芳基产物的合成在中度至良好的产率，并且耐受多种官能团，包括烷基，苯基，甲氧基，氟和氯基团。
• 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。
• Palladium-Catalyzed Direct Arylation of Polyfluoroarenes with Organosilicon Reagents
  作者：Huixin Fan、Yaping Shang、Weiping Su

  DOI：10.1002/ejoc.201402091

  日期：2014.6

  The palladium-catalyzed direct arylation of polyfluoroarenes with organosilicon reagents was achieved by establishing general reaction conditions. This protocol was compatible with a broad range of functional groups and offered the desired products in moderate to good yields.

  通过建立一般反应条件，实现了钯催化的多氟芳烃与有机硅试剂的直接芳基化反应。该协议与广泛的官能团兼容，并以中等至良好的产量提供所需的产品。
• Palladium-catalyzed direct arylation of polyfluoroarene and facile synthesis of liquid crystal compounds
  作者：Xiaowei Ma、Yan Liu、Ping Liu、Jianwei Xie、Bin Dai、Zhiyong Liu

  DOI：10.1002/aoc.3106

  日期：2014.3

  zed direct arylation of polyfluoroarenes with aromatic halides in the presence of Cs2CO3 as base and toluene as solvent. In most cases, the desired arylated products of aromatic bromides were obtained in good to excellent yield at 80°C, and aryl chlorides also gave modest to good yields of arylated products at 110°C. According to this efficient C―C bondforming method, polyfluorobiphenyl liquid crystal

  在Cs 2 CO 3为碱和甲苯为溶剂的情况下，已经开发了一种简便的方法来制备Pd（OAc）2 / PCy 3催化的多氟芳烃与芳族卤化物的直接芳基化，制备多氟联苯。在大多数情况下，所需的芳族溴化芳基化产物在80℃时具有良好至极佳的收率，而芳基氯化物在110℃下也具有中等至良好收率的芳基化产物。根据这种有效的C-C键形成方法，通过Pd催化多氟芳烃与长烷基链取代的芳基溴化物的直接芳基化反应，制备了多氟联苯液晶化合物，产率为62-96％。版权所有©2014 John Wiley＆Sons，Ltd.