N,N'-di(propan-2-yl)-2,6-bis[4-(2-trimethylsilylethynyl)phenyl]benzenecarboximidamide | 948026-02-6

• 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'-di(propan-2-yl)-2,6-bis[4-(2-trimethylsilylethynyl)phenyl]benzenecarboximidamide
• CAS: 948026-02-6
• 化学式: C₃₅H₄₄N₂Si₂
• 分子量: 548.919
• InChiKey: UBVZAZUUVCVZDL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.63
• 重原子数：
  39
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.34
• 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'-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
• 作为产物：
  描述：

  2'-Iodo-4,4''-bis-trimethylsilanylethynyl-[1,1';3',1'']terphenyl 、 N,N'-二异丙基碳二亚胺 在 正丁基锂 、 四甲基乙二胺 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 10.0h， 以48%的产率得到N,N'-di(propan-2-yl)-2,6-bis[4-(2-trimethylsilylethynyl)phenyl]benzenecarboximidamide
  参考文献：
  名称：

  催化不对称反应的互补双螺旋分子的对映选择性合成。

  摘要：

  DOI：

  10.1002/anie.200701735

文献信息

• 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.
• 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