Chiral resolution of monosaccharides as 1-phenyl-3-methyl-5-pyrazolone derivatives by ligand-exchange CE using borate anion as a central ion of the chiral selector
Chiral resolution of monosaccharides as 1-phenyl-3-methyl-5-pyrazolone derivatives by ligand-exchange CE using borate anion as a central ion of the chiral selector
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DOI：
10.1002/elps.200600140
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发表时间：
2006-12-01
期刊：
影响因子：
2.9
通讯作者：
Yamamoto, Atsushi
中科院分区：
文献类型：
--
作者：
Kodama, Shuji;Aizawa, Sen-ichi;Yamamoto, Atsushi
以1-苯基-3-甲基-5-吡唑啉酮（PMP）为手性选择剂，以硼酸根离子为中心离子，（S）-3-氨基-1，2-丙二醇（SAP）为手性选择剂配体，研究了6种还原性单糖（甘露糖、半乳糖、岩藻糖、葡萄糖、木糖和阿拉伯糖）的衍生化及其手性拆分。PMP-甘露糖、PMP-半乳糖和PMP-岩藻糖均成功地实现了对映体分离。降低毛细管温度可提高PMP-甘露糖体系的分离度，降低PMP-半乳糖和PMP-岩藻糖体系的分离度。而在PMP-甘露糖体系中，在pH 8.9时获得最大分离度，在PMP-半乳糖和PMP-岩藻糖体系中，分离度随着pH的增加而逐渐增加。考虑到CE实验中SAP和PMP-单糖与硼酸盐形成三元配合物，通过半经验分子轨道计算得到了硼酸盐非对映异构体的优化结构，讨论了非对映异构体的结构差异与对映体分离行为的关系。
Six reducing monosaccharides (mannose, galactose, fucose, glucose, xylose, and arabinose) were derivatized with 1-phenyl-3-methyl-5-pyrazolone (PMP) and chiral resolution of these racemic PMP-monosaccharides was studied by ligand-exchange CE using borate anion as a central ion of the chiral selector and (S)-3-amino-1,2-propanediol (SAP) as a chiral selector ligand. PMP-mannose, PMP-galactose and PMP-fucose were successfully enantioseparated. Lowering the capillary temperature increased the resolution of PMP-mannose system, but decreased that of PMP-galactose and PMP-fucose systems. Whereas the maximum resolution was obtained at pH 8.9 in the PMP-mannose system, resolution increased gradually with pH in the PMP-galactose and PMP-fucose systems. Expecting the formation of the ternary borate complexes with SAP and PMP-monosaccharide in the CE experiments, the optimized structures of the borate diastereomers were obtained by semiempirical molecular orbital calculations to discuss the structural difference of the diastereomers in connection with the enantioseparation behaviors.