2-(4-Ethynylphenyl)-6-[4-(2-trimethylsilylethynyl)phenyl]benzoic acid | 862801-90-9

• 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-(4-Ethynylphenyl)-6-[4-(2-trimethylsilylethynyl)phenyl]benzoic acid
• 英文别名: 2-(4-ethynylphenyl)-6-[4-(2-trimethylsilylethynyl)phenyl]benzoic acid
• CAS: 862801-90-9
• 化学式: C₂₆H₂₂O₂Si
• 分子量: 394.545
• InChiKey: PWQFAVCYSVZRKI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.93
• 重原子数：
  29
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(4-Ethynylphenyl)-6-[4-(2-trimethylsilylethynyl)phenyl]benzoic acid 在 bis-triphenylphosphine-palladium(II) chloride copper(l) iodide 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 14.0h， 以64%的产率得到2-[4-[4-[4-[2-Carboxy-3-[4-(2-trimethylsilylethynyl)phenyl]phenyl]phenyl]buta-1,3-diynyl]phenyl]-6-[4-(2-trimethylsilylethynyl)phenyl]benzoic acid
  参考文献：
  名称：

  人工双螺旋的模块化策略。

  摘要：

  DOI：

  10.1002/anie.200501028
• 作为产物：
  描述：

  2,6-Bis[4-(2-trimethylsilylethynyl)phenyl]benzoic acid 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 以35%的产率得到2-(4-Ethynylphenyl)-6-[4-(2-trimethylsilylethynyl)phenyl]benzoic acid
  参考文献：
  名称：

  人工双螺旋的模块化策略。

  摘要：

  DOI：

  10.1002/anie.200501028

文献信息

• Synthesis of Complementary Double-Stranded Helical Oligomers through Chiral and Achiral Amidinium−Carboxylate Salt Bridges and Chiral Amplification in Their Double-Helix Formation
  作者：Hiroshi Ito、Masato Ikeda、Takashi Hasegawa、Yoshio Furusho、Eiji Yashima

  DOI：10.1021/ja108514t

  日期：2011.3.16

  acetylide complex regions, indicating that the chiral substituents on the amidine units biased a helical sense preference. The Cotton effect patterns and intensities were highly dependent on the molecular lengths. The complementary double-helix formation was also explored using the chiral/achiral amidine strands with different sequences in which a chiral amidine unit was introduced at the center (center-chiral)

  通过顺序逐步反应合成了一系列从2-mer到5-mer的互补分子链，由带有手性/手性脒或非手性羧基的间三联苯单元通过Pt（II）乙炔配合物连接，并具有手性通过圆二色性（CD）和（1）H NMR光谱研究了双螺旋形成。在 CHCl(3) 中，由 (R)- 或 (S)- 脒单元组成的“全手性”脒链与互补的非手性羧酸链通过脒-羧酸盐桥形成优先手双螺旋，导致Pt(II) 乙炔络合物区域中的特征诱导 CD，表明脒单元上的手性取代基偏向于螺旋有义偏好。棉花效应模式和强度高度依赖于分子长度。还使用具有不同序列的手性/非手性脒链探索互补双螺旋的形成，其中在脒链的中心（中心-手性）或末端（边缘-手性）引入手性脒单元。通过比较CD强度与相应的全手性脒双螺旋的CD强度，研究了手性和非手性脒单元的序列对双螺旋形成中手性放大（“中士和士兵”效应）的影响具有相同的分子长度。全手性和手性/手性脒双链体的变温 CD 实验表明
• Photoresponsive double-stranded helices composed of complementary strands
  作者：Yoshio Furusho、Yoshie Tanaka、Takeshi Maeda、Masato Ikeda、Eiji Yashima

  DOI：10.1039/b705347a

  日期：——

  A photoresponsive single-handed double helical supramolecule composed of complementary strands bearing azobenzene moieties underwent a reversible trans–cis-isomerization regulated by photoirradiation, resulting in a change in its molecular length.

  由带有偶氮苯分子的互补链组成的光致发光单手双螺旋超分子在光照射的调节下发生了可逆的反式-顺式-异构化，从而导致其分子长度发生变化。
• Double Helix-to-Double Helix Transformation, Using Platinum(II) Acetylide Complexes as Surrogate Linkers
  作者：Yoshio Furusho、Yoshie Tanaka、Eiji Yashima

  DOI：10.1021/ol0608294

  日期：2006.6.1

  active double helices consisting of complementary strands stabilized by amidinium-carboxylate salt bridges. The m-terphenyl groups of each strand are joined by trans-Pt(II) acetylide complexes with pendant PPh(3) ligands as the surrogate linker, which converts to cis counterparts by a ligand exchange reaction with cis-1,2-bis(diphenylphosphino)ethylene, resulting in the formation of double helices

  我们描述了新颖的光学活性双螺旋，由complementary链-羧酸盐盐桥稳定的互补链组成。每条链的m-三联苯基通过反式Pt（II）乙炔化物络合物与PPh（3）侧基配体作为替代连接基连接，通过与顺式1,2-双（二苯基膦基）乙烯，导致形成具有不同结构的双螺旋。随后碘促进的Pt（II）原子上的还原消除反应生成了完全有机的，对映体纯的双螺旋。[结构：见文字]
• Thermodynamic and Kinetic Stabilities of Complementary Double Helices Utilizing Amidinium–Carboxylate Salt Bridges
  作者：Hidekazu Yamada、Zong-Quan Wu、Yoshio Furusho、Eiji Yashima

  DOI：10.1021/ja303701d

  日期：2012.6.6

  A series of dimer strands consisting of m-terphenyl backbones bearing complementary chiral or achiral amidines and achiral carboxylic acid residues connected by various types of linkers, such as diacetylene, Pt(II)-acetylide, and p-diethynylbenzene linkages, were synthesized by a modular strategy, and their chiroptical properties on the complementary double helix formations were investigated by absorption, circular dichroism (CD), and H-1 NMR spectroscopies. The thermodynamic and kinetic stabilities of the complementary double helices assisted by amidinium-carboxylate salt bridges are highly dependent on their linkages, and the thermodynamic analyses of the dimer duplexes revealed that the association constants increased in the order: Pt(II)-acetylide linker < p-diethynylbenzene linker < diacetylene linker, which is in agreement with the reverse order of their bulkiness. The substituents on the amidine groups were also found to affect the stabilities on the duplexes and the association constants increased in the order: isopropyl < (R)-1-phenylethyl < cyclohexyl. In addition, the introduction of electron-donating and/or electron-withdrawing substituents at the phenyl groups of the p-diethynylbenzene linkers connecting the amidine and carboxylic acid units, respectively, tends to stabilize the complementary double helices, especially in polar solvents, such as DMSO, due to the attractive charge-transfer interactions between the aromatic linkers, although the salt bridge formation is hampered in DMSO. Furthermore, the kinetic analyses of the chain exchange reactions for the duplexes bearing diacetylene and p-diethynylbenzene linkages showed that these were slow processes with negative Delta S-double dagger values, meaning that the chain exchange reactions proceed via direct exchange pathways. In contrast, those for the duplexes bearing Pt(II)-acetylide linkages were fast processes supported by positive Delta S-double dagger values, suggesting that the chain exchange reactions proceed via dissociation-exchange ones. The helix-inversion kinetics investigated for the racernic dimer duplexes composed of achiral amidines based on variable-temperature H-1 NMR measurements indicated that the barriers for the helix-inversion increased in the order: Pt(II)-acetylide linker, p-diethynylbenzene linker < diacetylene linker.