Molecular Mechanisms of Dielectrically Controlled Resolution (DCR).
Molecular Mechanisms of Dielectrically Controlled Resolution (DCR).
复制标题
介电控制分辨率 (DCR) 的分子机制。
DOI：
10.1007/128_071
复制
发表时间：
2007
影响因子：
8.6
通讯作者：
N. Hirayama
中科院分区：
文献类型：
--
作者：
K. Sakai;R. Sakurai;N. Hirayama
人们普遍认为，手性辨别过程完全取决于相关分子的立体化学。然而，通过对几种具有流行手性选择器的拆分系统进行系统研究，我们发现了一个新事实，它引发了对这种流行的手性拆分概念的修改。研究表明，手性选择器的一种对映体可以在具有不同介电常数的不同溶剂系统中识别目标分子的两种对映体。这种现象被称为介电控制分辨率 (DCR)。由于 DCR 在不同的分辨率系统中观察到，并且对于特定系统不太具体，因此预计 DCR 会广泛出现在各种分辨率系统中。我们基于相关非对映体盐的 X 射线分析，研究了这一有趣现象背后的分子机制。所公开的机制清楚地表明，手性选择器可以固有地识别目标分子的两种对映体，并且只有拆分过程中使用的溶剂的介电性质决定对映体的选择。
It is widely believed that the chiral discrimination process is solely dependent on the stereochemistryof the relevant molecules. However, through systematic studies on several resolution systems with popularchiral selectors, we have discovered a new fact that triggers modification of this prevailing conceptof chiral resolution. The studies have demonstrated that one enantiomer of a chiral selector can recognizeboth enantiomers of a target molecule in different solvent systems with different dielectric constants.The phenomenon was termed dielectrically controlled resolution (DCR). Since DCR was observed in differentresolution systems and was not too specific to a particular system, DCR was expected to widely occurin various resolution systems. We have investigated the molecular mechanism underlying this interestingphenomenon based on X-ray analysis of the relevant diastereomeric salts. The disclosed mechanism clearlyindicates that a chiral selector can inherently recognize both enantiomers of a target moleculeand only the dielectric property of the solvent employed in the resolution process governs the selectionof the enantiomer.