Storch Golo, Haas Maren, Trapp Oliver
Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstr. 5-13, 81377, München, Germany.
Max-Planck-Institute for Astronomy, Königstuhl 17, 69117, Heidelberg, Germany.
Chemistry. 2017 Apr 24;23(23):5414-5418. doi: 10.1002/chem.201700461. Epub 2017 Apr 3.
The rapid and direct determination of enantiomeric ratios is of increasing interest due to the significantly reduced effort compared to chromatographic methods and the large number of analytes, for instance in enantioselective catalysis. Current strategies include colorimetric assays, (a)chiral solvating reagents for NMR spectroscopy and metal complexes for CD sensing. We report the determination of enantiomeric ratios based on the self-induced diastereomeric anisochronism (SIDA) effect. Alanine derivatives that represent chiral products of enantioselective catalysis, such as the well-established hydrogenation of dehydroamino acids, were investigated. The SIDA effect was significantly enhanced by attachment of 3,5-dinitrobenzoyl π-π interactions sites. This simple modification enabled simultaneous determination of enantiomeric ratios and conversions by NMR spectroscopy.
与色谱方法相比，对映体比例的快速直接测定因其所需工作量显著减少以及分析物数量众多（例如在对映选择性催化中）而越来越受到关注。目前的策略包括比色测定、用于核磁共振光谱的（非）手性溶剂化试剂以及用于圆二色光谱传感的金属配合物。我们报告了基于自诱导非对映体异时性（SIDA）效应的对映体比例测定方法。研究了代表对映选择性催化手性产物的丙氨酸衍生物，如成熟的脱氢氨基酸氢化反应产物。通过连接3,5-二硝基苯甲酰基π-π相互作用位点，SIDA效应得到显著增强。这种简单的修饰使得能够通过核磁共振光谱同时测定对映体比例和转化率。
