Rigid macrocyclic triamides as anion receptors:: Anion-dependent binding stoichiometries and 1H chemical shift changes
Rigid macrocyclic triamides as anion receptors:: Anion-dependent binding stoichiometries and 1H chemical shift changes
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DOI：
10.1021/ja034563x
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发表时间：
2003-08-27
影响因子：
15
通讯作者：
Hamilton, AD
中科院分区：
文献类型：
--
作者：
Choi, KH;Hamilton, AD
3‘-氨基-3-联苯基甲酸的环三酰胺易于分步合成，是一类具有较大中心空腔的新型阴离子受体。在有机溶剂中，这种大环与四面体阴离子的结合比球形或平面阴离子更强。电荷分布对称的阴离子的结合化学计量依赖于溶剂的极性，而四面体对甲苯磺酸盐在所研究的所有溶剂中以1：1的化学计量比结合到大环上。大循环中心空腔内侧质子的H-1核磁共振化学位移变化也取决于结合阴离子的几何形状。通过对无环三酰胺和具有分子内氢键的大环的对照研究，证实了聚合的氢键供体阵列对于大环与阴离子结合的重要性。
The cyclic triamide of 3'-amino-3-biphenylcarboxlic acid is readily synthesized in a stepwise manner and represents a novel class of anion receptors with a large central cavity. This macrocycle binds more strongly to tetrahedral anions than spherical or planar anions in organic solvents. The binding stoichiometries for anions with symmetrical charge distribution depend on the solvent polarity, while tetrahedral p-tosylate binds to the macrocycle with 1:1 stoichiometry in all solvents studied. The H-1 NMR chemical shift changes of the protons lining the interior of the macrocycle's central cavity also depend on the geometry of the bound anion. The importance of the convergent array of hydrogen bond donors for anion binding by the macrocycle was confirmed by control studies with an acyclic triamide and a macrocycle with intramolecular hydrogen bonds.