1,2-bis(4’-(N-Boc-aminomethylene)phenylene)ethyne | 1381949-73-0

• 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: 1,2-bis(4’-(N-Boc-aminomethylene)phenylene)ethyne
• 英文别名: ditert-butyl ((ethyne-1,2-diylbis(4,1-phenylene))bis(methylene))dicarbamate；tert-butyl N-[[4-[2-[4-[[(2-methylpropan-2-yl)oxycarbonylamino]methyl]phenyl]ethynyl]phenyl]methyl]carbamate
• CAS: 1381949-73-0
• 化学式: C₂₆H₃₂N₂O₄
• 分子量: 436.551
• InChiKey: NQWRWTPVPHPCFD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  32
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  76.7
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,2-bis(4’-(N-Boc-aminomethylene)phenylene)ethyne 在 (benzotriazo-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate 、 三氟乙酸 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 生成 N,N'-((ethyne-1,2-diylbis(4,1-phenylene))bis(methylene))bis(2-(5,8-di-tert-butyl-1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)acetamide)
  参考文献：
  名称：

  Degenerate Molecular Shuttles with Flexible and Rigid Spacers

  摘要：

  The preparation and dynamic behavior of degenerate rotaxane molecular shuttles are described in which a benzylic amide macrocycle moves back and forth between two naphthalimide-glycine units along a diphenylethyne spacer or an aliphatic spacer consisting of a C-9, C-12, or C-26 alkyl chain. Subtle differences in the H-1 NMR spectra of the rotaxanes can be related to the presence of conformers in which the macrocycle interacts simultaneously with both glycines, especially in the case of the C-9 spacer. The kinetic data of the shuttling behavior in the C-26 rotaxane were obtained from dynamic NMR spectroscopy. The Eyring activation parameters were found to be Delta H-double dagger = 10 +/- 1 kcal mol(-1), Delta S-double dagger = -6.5 +/- 2.0 cal mol(-1) K-1, Delta G(298)(double dagger) = 11.9 +/- 0.2 kcal mol(-1). For the systems with the shorter spacers, the shuttling rates were higher. Also in the diphenylethyne, rotaxane shuttling is rapid on the NMR time scale, indicating that the rigid unit does not impose a large barrier to the translocation of the macrocycle.

  DOI：

  10.1021/jo300907r
• 作为产物：
  描述：

  4-碘苄胺盐酸盐 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 四丁基氟化铵 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 27.0h， 生成 1,2-bis(4’-(N-Boc-aminomethylene)phenylene)ethyne
  参考文献：
  名称：

  Degenerate Molecular Shuttles with Flexible and Rigid Spacers

  摘要：

  The preparation and dynamic behavior of degenerate rotaxane molecular shuttles are described in which a benzylic amide macrocycle moves back and forth between two naphthalimide-glycine units along a diphenylethyne spacer or an aliphatic spacer consisting of a C-9, C-12, or C-26 alkyl chain. Subtle differences in the H-1 NMR spectra of the rotaxanes can be related to the presence of conformers in which the macrocycle interacts simultaneously with both glycines, especially in the case of the C-9 spacer. The kinetic data of the shuttling behavior in the C-26 rotaxane were obtained from dynamic NMR spectroscopy. The Eyring activation parameters were found to be Delta H-double dagger = 10 +/- 1 kcal mol(-1), Delta S-double dagger = -6.5 +/- 2.0 cal mol(-1) K-1, Delta G(298)(double dagger) = 11.9 +/- 0.2 kcal mol(-1). For the systems with the shorter spacers, the shuttling rates were higher. Also in the diphenylethyne, rotaxane shuttling is rapid on the NMR time scale, indicating that the rigid unit does not impose a large barrier to the translocation of the macrocycle.

  DOI：

  10.1021/jo300907r

文献信息

• The Delicate Balance of Preorganisation and Adaptability in Multiply Bonded Host-Guest Complexes
  作者：Larissa K. S. von Krbek、Andreas J. Achazi、Stefan Schoder、Marius Gaedke、Tobias Biberger、Beate Paulus、Christoph A. Schalley

  DOI：10.1002/chem.201605092

  日期：2017.2.24

  affinity in multiply bonded supramolecular complexes as they help reduce the entropic penalty of the binding event. This comes at the price that such rigid complexes are sensitive to small geometric mismatches. In marked contrast, nature uses more flexible building blocks. Thus, one might consider putting the rigidity/high‐affinity notion to the test. Multivalent crown/ammonium complexes are ideal for this

  刚性和预组织被认为是多重键合超分子复合物中高亲和力所必需的，因为它们有助于减少结合事件的熵损失。这是以这样的刚性复合物对小的几何失配敏感的代价为代价的。与此形成鲜明对比的是，自然界使用了更为灵活的构建基块。因此，可以考虑将“刚度/高亲和力”概念用于测试。多价冠/铵络合物对于此目的是理想的，因为单价相互作用是众所周知的。因此，已经分析了一系列具有不同间隔长度和刚性的二价络合物，以使螯合协同性和间隔物性质相互关联。与完全匹配的间隔物相比，间隔物过长会降低螯合剂的协同作用。但是，与预期相反，灵活的客人与螯合剂的结合力明显超过了刚性结构。柔性垫片可适应较小的几何形状的主客体不匹配。间隔物之间​​的相互作用有助于克服结合过程中构象固定的熵损失，并且在多价络合物中微妙的预组织和适应性平衡正在发挥作用。
• Degenerate Molecular Shuttles with Flexible and Rigid Spacers
  作者：D. Deniz Günbaş、Albert M. Brouwer

  DOI：10.1021/jo300907r

  日期：2012.7.6

  The preparation and dynamic behavior of degenerate rotaxane molecular shuttles are described in which a benzylic amide macrocycle moves back and forth between two naphthalimide-glycine units along a diphenylethyne spacer or an aliphatic spacer consisting of a C-9, C-12, or C-26 alkyl chain. Subtle differences in the H-1 NMR spectra of the rotaxanes can be related to the presence of conformers in which the macrocycle interacts simultaneously with both glycines, especially in the case of the C-9 spacer. The kinetic data of the shuttling behavior in the C-26 rotaxane were obtained from dynamic NMR spectroscopy. The Eyring activation parameters were found to be Delta H-double dagger = 10 +/- 1 kcal mol(-1), Delta S-double dagger = -6.5 +/- 2.0 cal mol(-1) K-1, Delta G(298)(double dagger) = 11.9 +/- 0.2 kcal mol(-1). For the systems with the shorter spacers, the shuttling rates were higher. Also in the diphenylethyne, rotaxane shuttling is rapid on the NMR time scale, indicating that the rigid unit does not impose a large barrier to the translocation of the macrocycle.