Detection and Chiral Recognition of α-Hydroxyl Acid through 1H and CEST NMR Spectroscopy Using a Ytterbium Macrocyclic Complex
Detection and Chiral Recognition of α-Hydroxyl Acid through 1H and CEST NMR Spectroscopy Using a Ytterbium Macrocyclic Complex
复制标题
使用镱大环配合物通过 H-1 和 CEST NMR 光谱检测和手性识别 α-羟基酸
DOI：
10.1002/anie.201912072
复制
发表时间：
2019-10-30
影响因子：
16.6
通讯作者：
Zhang, Hongjie
中科院分区：
文献类型：
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作者：
He, Haonan;Zhao, Kelu;Zhang, Hongjie
手性-羟基酸在化学合成中具有重要意义。目前用H-1核磁共振识别它们手性的方法受到其化学位移差小和在有机溶剂中的固有溶解度问题的限制。在此，我们开发了三个YbDO3A(ala)(3)衍生物，通过H-1 NMR和化学交换饱和转移（CEST）光谱识别水溶液中四种不同的市售手性α -羟基酸。质子核磁共振和CEST核磁共振观察到的手性α -羟基酸的位移差分别在15-40和20-40 ppm之间。我们的工作首次证明，即使是环的侧臂链上的一个手性中心也可以为其他两个非手性侧链的旋转提供条件。这是由于该结构的能态较低。结果表明，手性ybdo3a样配合物可以识别手性α -羟基酸，并具有明显的信号差异。
Chiral alpha-hydroxyl acids are of great importance in chemical synthesis. Current methods for recognizing their chirality by H-1 NMR are limited by their small chemical shift differences and intrinsic solubility problem in organic solvents. Herein, we developed three YbDO3A(ala)(3) derivatives to recognize four different commercially available chiral alpha-hydroxyl acids in aqueous solution through H-1 NMR and chemical exchange saturation transfer (CEST) spectroscopy. The shift difference between chiral alpha-hydroxyl acid observed by proton and CEST NMR ranged from 15-40 and 20-40 ppm, respectively. Our work demonstrates for first time, that even one chiral center on the side-arm chain of cyclen could set the stage for rotation of the other two non-chiral side chains into a preferred position. This is ascribed to the lower energy state of the structure. The results show that chiral YbDO3A-like complexes can be used to discriminate chiral alpha-hydroxyl acids with a distinct signal difference.