methyl 4’-(methylthio)-[1,1’-biphenyl]-4-carboxylate

• 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: methyl 4’-(methylthio)-[1,1’-biphenyl]-4-carboxylate
• 英文别名: methyl 4'-(methylthio)-[1,1'-biphenyl]-4-carboxylate；Methyl 4-(4-methylsulfanylphenyl)benzoate
• 化学式: C₁₅H₁₄O₂S
• 分子量: 258.341
• InChiKey: NIHHWBVDHLFISA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  4-氨甲基苯甲酸甲酯盐酸盐 在 N,N-二异丙基乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 methyl 4’-(methylthio)-[1,1’-biphenyl]-4-carboxylate
  参考文献：
  名称：

  由无痕连接体引导的无金属芳基交叉偶联。

  摘要：

  无金属、高选择性的联芳基化合物的合成对有机合成提出了重大挑战。报道了一种有前景的（杂）联芳基新方法的范围和机制，该方法通过将芳基取代基与无痕磺酰胺连接体（光剪接）进行光化学融合来实现。用不同的反应条件研究光剪接并对不同的合成探针（40 个例子，包括一组杂环）进行比较表明，该反应具有令人惊讶的广泛范围，并且既不涉及金属也不涉及自由基。量子化学计算表明CC键是通过分子内光化学过程形成的，该过程涉及激发单线态和五元过渡态的遍历，因此具有一致的ipso-ipso耦合结果。这些结果表明，光剪接是一种独特的激发态芳基交叉偶联方法，可用于合成多种联芳基化合物。

  DOI：

  10.1002/chem.201903582

文献信息

• [EN] METHOD FOR THE METAL-FREE PREPARATION OF A BIARYL BY A PHOTOSPLICING REACTION AND THEIR USES<br/>[FR] PROCÉDÉ DE PRÉPARATION SANS MÉTAL D'UN BIARYLE PAR RÉACTION DE PHOTOCOLLAGE ET UTILISATIONS ASSOCIÉES
  申请人：LEIBNIZ INST FUER NATURSTOFF FORSCHUNG UND INFEKTIONSBIOLOGIE E V HANS KNOELL INST HKI

  公开号：WO2019101679A1

  公开（公告）日：2019-05-31

  The present invention relates to a method for the metal-free preparation of a biaryl compound by a photosplicing reaction and its use in the preparation of chemical compounds, preferably of active ingredients e.g. in the fields of pharmaceuticals and agrochemicals. In particular, it refers to a method for the regiocontrolled preparation of a biaryl compound of formula (I): Ar-Ar' by photochemically reacting a precursor compound of formula (II): Ar-L-Ar' to form a biaryl compound of general formula: Ar-L-Ar' (II) → Ar-Ar' (I) wherein Ar and Ar', independently of each other, represent an unsubstituted or substituted C6-C20 aryl group or a heteroaryl group with 5–20 ring atoms selected from carbon, nitrogen, oxygen and sulfur, and L represents a group –X–Y–Z– as defined herein. The biaryl compounds are generally suitable as intermediates or key building blocks in a very broad spectrum of organic chemical syntheses and their respective utilities. Their use within the field of synthesis of active ingredients is an aspect of the invention, and their use in the preparation of pharmaceutically active ingredients is particularly preferred.

  本发明涉及一种通过光切割反应无金属制备联芳烃化合物的方法，以及其在化学化合物制备中的用途，特别是在制药和农药领域中的活性成分的制备中的用途。具体而言，它涉及一种通过光化学反应化学前体化合物（II）：Ar-L-Ar'与形成一般式的联芳烃化合物（II）→Ar-Ar'（I）反应，从而实现联芳烃化合物（I）的区域控制制备的方法，其中Ar和Ar'分别表示未取代或取代的C6-C20芳基或由碳、氮、氧和硫选择的5-20个环原子的杂芳基，L表示如本文所定义的一个组-X-Y-Z-。这些联芳烃化合物通常适用于有机化学合成的广泛领域中的中间体或关键构建块，以及它们各自的用途。它们在活性成分合成领域中的用途是本发明的一个方面，它们在制备药用活性成分中的用途尤为理想。
• Tackling poison and leach: catalysis by dangling thiol–palladium functions within a porous metal–organic solid
  作者：Bo Gui、Ka-Kit Yee、Yan-Lung Wong、Shek-Man Yiu、Matthias Zeller、Cheng Wang、Zhengta Xu

  DOI：10.1039/c5cc00140d

  日期：——

  Dangling thiol groups effectively anchor Pd(ii) atoms in a Zr(iv)-based MOF for multiple cycles of non-leaching heterogeneous catalysis.

  悬垂的硫醇基团有效地锚定了Pd（II）原子在基于Zr（IV）的MOF中，可进行多次非流失的异相催化反应。
• Method for the metal-free preparation of a biaryl by a photosplicing reaction and their uses
  申请人：Leibniz-Institut für Naturstoff-Forschung und Infektionsbiologie E. V. Hans-Knöll-Institut (HKI)

  公开号：US11485721B2

  公开（公告）日：2022-11-01

  The present invention relates to a method for the metal-free preparation of a biaryl compound by a photosplicing reaction and its use in the preparation of chemical compounds, preferably of active ingredients e.g. in the fields of pharmaceuticals and agrochemicals. In particular, it refers to a method for the regiocontrolled preparation of a biaryl compound of formula (I): Ar—Ar′ by photochemically reacting a precursor compound of formula (II): Ar—L—Ar′ to form a biaryl compound of general formula: Ar—L—Ar′(II)→Ar—Ar′ (I) wherein Ar and Ar′, independently of each other, represent an unsubstituted or substituted C6-C20 aryl group or a heteroaryl group with 5-20 ring atoms selected from carbon, nitrogen, oxygen and sulfur, and L represents a group —X—Y—Z— as defined herein. The biaryl compounds are generally suitable as intermediates or key building blocks in a very broad spectrum of organic chemical syntheses and their respective utilities. Their use within the field of synthesis of active ingredients is an aspect of the invention, and their use in the preparation of pharmaceutically active ingredients is particularly preferred.

  本发明涉及一种通过光聚合反应无金属制备双芳基化合物的方法，以及该方法在制备化 学化合物，尤其是在医药和农用化学品领域制备活性成分中的应用。具体而言，本发明涉及一种式（I）双芳基化合物的受控制备方法：Ar-Ar′，使式（II）的前体化合物发生光化学反应：Ar-L-Ar′ 光化学反应生成通式为：Ar-L-Ar′(Ⅱ)→Ar-Ar′(Ⅰ) 其中 Ar 和 Ar′彼此独立地代表未取代或取代的 C6-C20 芳基或具有 5-20 个选自碳、氮、氧和硫的环原子的杂芳基，L 代表本文定义的基团-X-Y-Z-。双芳基化合物通常可作为非常广泛的有机化学合成及其各自用途的中间体或关键构件。它们在活性成分合成领域中的应用是本发明的一个方面，特别优选它们在制备药物活性成分中的应用。
• METHOD FOR THE METAL-FREE PREPARATION OF A BIARYL BY A PHOTOSPLICING REACTION AND THEIR USES
  申请人：Leibniz-lnstitut fur Naturstoff-Forschung und Infektionsbiologie E.V.Hans-Knoll-lnstitut (HKI)

  公开号：US20200339529A1

  公开（公告）日：2020-10-29

  The present invention relates to a method for the metal-free preparation of a biaryl compound by a photosplicing reaction and its use in the preparation of chemical compounds, preferably of active ingredients e.g. in the fields of pharmaceuticals and agrochemicals. In particular, it refers to a method for the regiocontrolled preparation of a biaryl compound of formula (I): Ar—Ar′ by photochemically reacting a precursor compound of formula (II): Ar—L—Ar′ to form a biaryl compound of general formula: Ar—L—Ar′(II)→Ar—Ar′ (I) wherein Ar and Ar′, independently of each other, represent an unsubstituted or substituted C6-C20 aryl group or a heteroaryl group with 5-20 ring atoms selected from carbon, nitrogen, oxygen and sulfur, and L represents a group —X—Y—Z— as defined herein. The biaryl compounds are generally suitable as intermediates or key building blocks in a very broad spectrum of organic chemical syntheses and their respective utilities. Their use within the field of synthesis of active ingredients is an aspect of the invention, and their use in the preparation of pharmaceutically active ingredients is particularly preferred.
• LiO-t-Bu/CsF-Mediated Formal Hydrolysis of Trifluoromethyl Arenes
  作者：Masanori Shigeno、Moe Kiriyama、Koki Izumi、Keita Sasaki、Ozora Sasamoto、Kanako Nozawa-Kumada、Yoshinori Kondo

  DOI：10.1055/a-2236-0209

  日期：2024.5

  hydrolysis of trifluoromethyl arenes without deprotonation functionality utilizing a combined Brønsted base system comprising LiO-t-Bu and CsF. The reaction conditions were optimized using 4-(trifluoromethyl)biphenyl as the model substrate, achieving a 94% yield with LiO-t-Bu/CsF. The scope of the substrate was explored, demonstrating the applicability of the system to various functionalities, such as (hetero)aryl