Rudzińska-Szostak Ewa, Górecki Łukasz, Berlicki Łukasz, Ślepokura Katarzyna, Mucha Artur
Department of Bioorganic Chemistry, Faculty of Chemistry, Wrocław University of Technology, Wrocław, Poland.
Faculty of Chemistry, University of Wrocław, Wrocław, Poland.
Chirality. 2015 Oct;27(10):752-60. doi: 10.1002/chir.22494. Epub 2015 Aug 25.
Because of their unique 3D arrangement, naturally occurring Cinchona alkaloids and their synthetic derivatives have found wide-ranging applications in chiral recognition. Recently, we determined the enantioselective properties of C-9-phosphate mixed triesters of quinine as versatile chiral solvating agents in nuclear magnetic resonance (NMR) spectroscopy. In the current study, we introduce new zwitterionic members of this class of molecules containing a negatively charged phosphate moiety (i.e., ethyl, n-butyl and phenyl hydrogen quininyl phosphate). An efficient approach for synthesizing these compounds is elaborated, and full characterization, including conformational and autoaggregation phenomena studies, was performed. Therefore, their ability to induce NMR anisochrony of selected enantiomeric substrates (i.e., primarily N-DNB-protected amino acids and their methyl esters) was analyzed compared to uncharged diphenyl quininyl phosphate and its positively charged quaternary ammonium hydrochloride salt. In addition, (1) H and (13) C NMR experiments revealed their enantiodiscrimination potential toward novel analytes, such as secondary amines and nonprotected amino acids.
由于其独特的三维排列方式，天然存在的金鸡纳生物碱及其合成衍生物在手性识别方面有着广泛的应用。最近，我们确定了奎宁的C-9-磷酸混合三酯作为核磁共振（NMR）光谱中通用的手性溶剂化剂的对映选择性特性。在当前的研究中，我们引入了这类分子的新两性离子成员，其含有带负电荷的磷酸部分（即乙基、正丁基和苯基氢奎宁基磷酸酯）。阐述了一种合成这些化合物的有效方法，并进行了全面表征，包括构象和自聚集现象研究。因此，与不带电荷的二苯基奎宁基磷酸酯及其带正电荷的季铵盐酸盐相比，分析了它们诱导选定对映体底物（即主要是N-DNB保护的氨基酸及其甲酯）的NMR非等时性的能力。此外，（1）H和（13）C NMR实验揭示了它们对新型分析物（如仲胺和未保护的氨基酸）的对映体识别潜力。
