2-(4-ethynylphenyl)-N,N'-di(propan-2-yl)-6-[4-(2-trimethylsilylethynyl)phenyl]benzenecarboximidamide | 948026-03-7

• 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)-N,N'-di(propan-2-yl)-6-[4-(2-trimethylsilylethynyl)phenyl]benzenecarboximidamide
• CAS: 948026-03-7
• 化学式: C₃₂H₃₆N₂Si
• 分子量: 476.737
• InChiKey: SVFXWVFAFCJAEL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.38
• 重原子数：
  35
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  24.4
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-(4-ethynylphenyl)-N,N'-di(propan-2-yl)-6-[4-(2-trimethylsilylethynyl)phenyl]benzenecarboximidamide 在 copper(l) iodide (C₂H₅)2NH 、 tetra-n-butylammonium fluoride 作用下， 以 四氢呋喃 、 氯仿 为溶剂， 生成
  参考文献：
  名称：

  通过手性和非手性脒-羧酸盐桥合成互补双链螺旋低聚物并在其双螺旋形成中进行手性扩增

  摘要：

  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

  DOI：

  10.1021/ja108514t
• 作为产物：
  描述：

  N,N'-di(propan-2-yl)-2,6-bis[4-(2-trimethylsilylethynyl)phenyl]benzenecarboximidamide 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 生成 2-(4-ethynylphenyl)-N,N'-di(propan-2-yl)-6-[4-(2-trimethylsilylethynyl)phenyl]benzenecarboximidamide
  参考文献：
  名称：

  Thermodynamic and Kinetic Stabilities of Complementary Double Helices Utilizing Amidinium–Carboxylate Salt Bridges

  摘要：

  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.

  DOI：

  10.1021/ja303701d

文献信息

• Diastereoselective Imine-Bond Formation through Complementary Double-Helix Formation
  作者：Hidekazu Yamada、Yoshio Furusho、Eiji Yashima

  DOI：10.1021/ja301430h

  日期：2012.5.2

  different stereostructures are synthesized and used as templates for diastereoselective imine-bond formations between two achiral carboxylic acid monomers bearing a terminal aldehyde group and racemic 1,2-cyclohexanediamine, resulting in a preferred-handed double helix stabilized by complementary salt bridges. The diastereoselectivity of the racemic amine is significantly affected by the chirality of

  合成了具有不同立体结构的各种手性和非手性接头的旋光脒二聚体链，并将其用作模板，用于在两个带有末端醛基的非手性羧酸单体和外消旋 1,2-环己二胺之间形成非对映选择性亚胺键，从而得到通过互补盐桥稳定的首选双螺旋。外消旋胺的非对映选择性受到脒残基手性以及模板中接头的刚性和/或手性的显着影响。核磁共振和动力学研究表明，目前的亚胺键形成涉及两步可逆反应。
• Enantioselective Synthesis of Complementary Double-Helical Molecules that Catalyze Asymmetric Reactions
  作者：Takashi Hasegawa、Yoshio Furusho、Hiroshi Katagiri、Eiji Yashima

  DOI：10.1002/anie.200701735

  日期：2007.8.3
• 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.
• 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