N,N'-bis[(1R)-1-phenylethyl]-2,6-bis[4-(2-trimethylsilylethynyl)phenyl]benzenecarboximidamide | 862801-81-8

• 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: N,N'-bis[(1R)-1-phenylethyl]-2,6-bis[4-(2-trimethylsilylethynyl)phenyl]benzenecarboximidamide
• CAS: 862801-81-8
• 化学式: C₄₅H₄₈N₂Si₂
• 分子量: 673.061
• InChiKey: QLDPUHKZJGAOMR-VSJLXWSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.34
• 重原子数：
  49
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.22
• 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：

  N,N'-bis[(1R)-1-phenylethyl]-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 (R)-HC2C6H4C6H3(C6H4C2Si(CH3)3)C(NCH(CH3)C6H5)NHCH(CH3)C6H5
  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：

  1,3-二氯苯 在 正丁基锂 、 四甲基乙二胺 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 7.75h， 生成 N,N'-bis[(1R)-1-phenylethyl]-2,6-bis[4-(2-trimethylsilylethynyl)phenyl]benzenecarboximidamide
  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

• Double-Stranded Supramolecular Assembly through Salt Bridge Formation between Rigid and Flexible Amidine and Carboxylic Acid Strands
  作者：Hiroki Iida、Munenori Shimoyama、Yoshio Furusho、Eiji Yashima

  DOI：10.1021/jo902158v

  日期：2010.1.15

  A series of monomeric strands consisting of m-terphenyl backbones with chiral rigid C-linked (3) and flexible N-linked (5) formamidines and achiral carboxylic acid (4) and flexible carboxymethyl (6) residues were synthesized, and their duplex formations through amidinium−carboxylate salt bridges were investigated by NMR, circular dichroism (CD), and UV−visible spectroscopies. The salt bridge-derived

  一系列组成的单体链的米-三联苯骨架与手性刚性Ç -连接的（3）和柔性ñ -连接的（5）甲脒和非手性羧酸（4）和柔性羧甲基（6）残基进行合成，和它们的双工地层通过am-羧酸盐桥进行了NMR，圆二色性（CD）和UV可见光谱学研究。盐桥衍生的双链体的形成在很大程度上取决于甲am和羧酸链的结构，以及C-连接的甲am链3与柔性的N联甲am链5形成了更加稳定的互补羧酸链（4和6）的双链体。单晶X射线分析表明，双链体5·4具有偏斜的右手双螺旋结构。还通过由二乙炔连接基连接的5和4的二聚体合成了互补的双链体二聚体。可变温度CD测量表明，双链体具有由柔性N-连接的甲from单元产生的动态双螺旋结构。
• Photocontrolled template-directed synthesis of complementary double helices assisted by amidinium–carboxylate salt bridge formation
  作者：Junki Tanabe、Daisuke Taura、Hidekazu Yamada、Yoshio Furusho、Eiji Yashima

  DOI：10.1039/c3sc50833a

  日期：——

  chloroform in the presence of the corresponding optically inactive carboxylic acid dimer or optically active amidine dimer linked by a trans-azobenzene unit as the template, respectively. The cis-azobenzene-linked carboxylic acid template markedly slowed the monomer conversions, and hence a reversible photocontrolled dimerization was achieved by light-induced cis–trans isomerization upon alternative

  在一个末端带有甲酰基或氨基的手性or或非手性羧酸单体之间的模板指导的亚胺键形成反应显着地加速了34倍或10倍。 氯仿在分别以反式-偶氮苯单元为模板连接的相应的旋光性羧酸二聚体或旋光性am二聚体的存在下。所述顺-azobenzene联羧酸模板显着减缓了单体转化率，且因此可逆photocontrolled二聚化，通过光诱导的实现顺-反式在与UV和可见光照射替代异构化。
• Complementary double helix formation through template synthesis
  作者：Hidekazu Yamada、Yoshio Furusho、Hiroshi Ito、Eiji Yashima

  DOI：10.1039/c002170a

  日期：——

  The dimerization of carboxylic acid derivatives bearing an amino or a formyl group at one end was significantly enhanced in benzene in the presence of an optically active amidine dimer to afford a complementary double helix stabilized with salt bridges.

  在苯中，一端带有氨基或甲酰基团的羧酸衍生物在光学活性脒二聚体的存在下，其二聚化作用明显增强，从而产生了以盐桥稳定的互补双螺旋。
• 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
• 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.