De Los Santos Zeus A, Joyce Leo A, Sherer Edward C, Welch Christopher J, Wolf Christian
Department of Chemistry , Georgetown University , Washington , DC 20057 , United States.
Department of Process and Analytical Chemistry , Merck Research Laboratories , Rahway , New Jersey 07065 , United States.
J Org Chem. 2019 Apr 19;84(8):4639-4645. doi: 10.1021/acs.joc.8b01301. Epub 2018 Jul 27.
The determination of the enantiopurity and the concentration of chiral compounds by chiroptical sensing with molecular probes is increasingly attractive for high-throughput screening applications including streamlined asymmetric reaction development. In this study, we use stereodynamic aluminum biphenolate complexes for quantitative ee and concentration analysis of amino alcohols and α-hydroxy acids. An important feature of the tropos biphenolate ligand used is the presence of a phenylacetylene antenna for optimal chirality recognition and CD/UV responses at high wavelengths. The complexation-driven chirality amplification yields strong CD signals, which allows quantitative chiroptical sensing with good accuracy. We show that aluminate biphenolate sensors can exhibit linear and nonlinear correlations between the induced CD signals and the enantiomeric composition or concentration of the chiral substrate.
通过使用分子探针进行手性光学传感来测定手性化合物的对映体纯度和浓度，对于包括简化不对称反应开发在内的高通量筛选应用越来越具有吸引力。在本研究中，我们使用立体动力学双酚铝配合物对氨基醇和α-羟基酸进行对映体过量（ee）和浓度的定量分析。所使用的对流双酚配体的一个重要特征是存在苯乙炔天线，用于在高波长下实现最佳的手性识别和圆二色性（CD）/紫外（UV）响应。络合驱动的手性放大产生强烈的CD信号，这使得能够以良好的准确度进行定量手性光学传感。我们表明，铝酸双酚盐传感器在诱导的CD信号与手性底物的对映体组成或浓度之间可以表现出线性和非线性相关性。
