Synthesis of a novel cyclodextrin-derived chiral stationary phase with multiple urea linkages and enantioseparation toward chiral osmabenzene complex.
Synthesis of a novel cyclodextrin-derived chiral stationary phase with multiple urea linkages and enantioseparation toward chiral osmabenzene complex.
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DOI：
10.1016/j.chroma.2013.01.087
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发表时间：
2013-03
期刊：
影响因子：
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通讯作者：
Chun Lin;Wen-na Liu;Jun Fan;Yuekui Wang;S. Zheng;Ran Lin;Hui Zhang;Weiguang Zhang
中科院分区：
文献类型：
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作者：
Chun Lin;Wen-na Liu;Jun Fan;Yuekui Wang;S. Zheng;Ran Lin;Hui Zhang;Weiguang Zhang
通过Staudinger反应将七（6-叠氮基-6-脱氧-2，3-二-O-对氯苯氨甲酰基）-β-环糊精固定在硅胶表面，合成了一种新型手性固定相，并将其用于对一对锇苯配合物{Os[CHC（PPh 3）CHC（PPh 3）CH]（C9 H6 NO）2}Cl（1）的对映体拆分，这是迄今为止首次报道的手性金属锇苯配合物对映体拆分。详细考察了盐添加剂、有机改性剂、pH值、柱温等分离条件对络合物保留和拆分的影响。同时提出了可能的手性识别机理。在优化的条件下，通过半制备型手性HPLC技术对手性配合物1进行了拆分，并通过分析型HPLC、NMR光谱和溶液圆二色谱（CD）对两种纯对映体进行了表征。通过圆二色光谱的理论研究，证实了该对映体的绝对构型。
A novel chiral stationary phase was synthesized by immobilizing heptakis(6-azido-6-deoxy-2,3-di-O-p-chlorophenylcarbamoylated)-β-cyclodextrin onto silica gel surface via Staudinger reaction, and applied in enantiomeric separation of a pair of osmabenzene complexes, {Os[CHC(PPh3)CHC(PPh3)CH](C9H6NO)2}Cl (1), which is the first report for enantioseparation of the chiral-only-at-metal osmabenzene complex till now. The effects of separation conditions including salt additives, organic modifiers, pH values, and column temperature on the retention and resolution of the complex have been investigated in detail. Meanwhile, possible chiral recognition mechanism was presented. Chiral complex 1 was well resolved via semi-preparative chiral HPLC technique under optimization conditions and two pure enantiomers were further characterized by analytical HPLC, NMR spectra and solution circular dichroism (CD) spectra, respectively. Furthermore, absolute configuration of the enantiomer was confirmed by theoretical investigation of CD spectra.