Department of Chemistry and Chemistry Institute for Functional Materials, Pusan National University, Kuemjeong-Ku, Busan 609-735, South Korea.
J Chromatogr A. 2010 Oct 8;1217(41):6436-41. doi: 10.1016/j.chroma.2010.08.041. Epub 2010 Aug 22.
A ligand exchange chiral stationary phase (CSP) developed previously in this laboratory by bonding (R)-phenylglycinol derivative, sodium N-[(R)-2-hydroxy-1-phenylethyl]-N-undecylaminoacetate, to silica gel was successfully applied to the resolution of proton pump inhibitors (PPIs) including omeprazole, pantoprazole, lansoprazole and rabeprazole. For example, the separation factors (α) for the resolution of omeprazole, pantoprazole, lansoprazole and rabeprazole were 4.27, 5.28, 2.77 and 4.06, respectively, and the resolutions (R(S)) were 2.53, 2.55, 1.93, and 2.01, respectively, when 65% acetonitrile aqueous solution containing 0.5mM CuSO(4) and 0.05mM triethylamine was used as a mobile phase. Based on the chromatographic behaviors for the resolution of PPI analogues on CSP 1, a chiral recognition mechanism utilizing the sulfoxide oxygen and the benzimidazole ring nitrogen of PPIs as bidentate coordination donors to form an enantioselective ternary complex with the central Cu(II) ion and the chiral stationary bidentate ligand was proposed.
本实验室先前开发了一种配体交换手性固定相（CSP），通过将（R）-苯甘氨醇衍生物、N-[(R)-2-羟基-1-苯乙基]-N-十一烷基氨基乙酸钠键合到硅胶上，成功地应用于质子泵抑制剂（PPIs）的拆分，包括奥美拉唑、泮托拉唑、兰索拉唑和雷贝拉唑。例如，当以含有 0.5mM CuSO4 和 0.05mM 三乙胺的 65%乙腈水溶液为流动相时，奥美拉唑、泮托拉唑、兰索拉唑和雷贝拉唑的拆分分离因子（α）分别为 4.27、5.28、2.77 和 4.06，分辨率（R(S)）分别为 2.53、2.55、1.93 和 2.01。基于 CSP1 拆分 PPI 类似物的色谱行为，提出了一种手性识别机制，利用 PPIs 的亚砜氧和苯并咪唑环氮作为双配位供体，与中心 Cu(II)离子和手性固定双齿配体形成对映选择性的三元配合物。
