Department of Chemistry, Georgetown University, Washington, DC 20057, USA.
Chemistry. 2022 Nov 2;28(61):e202202028. doi: 10.1002/chem.202202028. Epub 2022 Aug 31.
A sterically encumbered aminoborane sensor is introduced and used for quantitative stereochemical analysis of monoalcohols, diols and amino alcohols. The small-molecule probe exhibits a rigid ortho-substituted arene scaffold with a proximate boron binding site and a triarylamine circular dichroism (CD) reporter unit which proved to be crucial for the observed chiroptical signal induction. Coordination of the chiral target molecule produces strong Cotton effects and UV changes that are readily correlated to its absolute configuration, enantiomeric composition and concentration to achieve comprehensive stereochemical analysis within a 5 % absolute error margin. The sensing method was successfully applied in the chromatography-free analysis of less than one milligram of a crude asymmetric reaction mixture and the advantages of this chiroptical sensing approach, which is amenable to high-throughput experimentation equipment and automation, over traditional methods is discussed.
本文介绍了一种空间位阻氨基硼烷传感器，并将其用于单醇、二醇和氨基醇的定量立体化学分析。该小分子探针具有刚性邻取代芳烃支架和紧邻硼结合位点的三芳基胺圆二色性（CD）报告单元，这对于观察到的手性光学信号诱导至关重要。手性目标分子的配位产生强的Cotton 效应和紫外变化，这些变化与绝对构型、对映体组成和浓度密切相关，可在 5%的绝对误差范围内实现全面的立体化学分析。该传感方法成功应用于不到一毫克的粗不对称反应混合物的无色谱分析，并且讨论了这种手性传感方法相对于传统方法的优势，它适用于高通量实验设备和自动化。
