L-脯氨酸衍生物为手性侧链的新型C2对称型手性固定相

doi:10.3724/SP.J.1123.2017.02029

色谱 ›› 2017, Vol. 35 ›› Issue (7): 703-711.DOI: 10.3724/SP.J.1123.2017.02029

L-脯氨酸衍生物为手性侧链的新型C₂对称型手性固定相

陈龙¹, 程玲平¹, 何珊珊¹, 何云超¹, 吴亚玲¹, 柯燕雄¹, 梁鑫淼^1,2

1. 华东理工大学药学院, 制药工程与过程化学教育部工程研究中心, 上海 200237;
2. 中国科学院大连化学物理研究所, 辽宁大连 116023

收稿日期:2017-02-25 出版日期:2017-07-08 发布日期:2013-10-18
通讯作者: 柯燕雄,Tel:(021)642506222,E-mail:key@ecust.edu.cn
基金资助:
国家自然科学基金项目（21375038）.

New C₂ symmetric chiral stationary phases based on L-proline derivatives as chains

CHEN Long¹, CHENG Lingping¹, HE Shanshan¹, HE Yunchao¹, WU Yaling¹, KE Yanxiong¹, LIANG Xinmiao^1,2

1. Engineering Research Center of Pharmaceutical Process Chemistry, Ministry of Education, School of Pharmacy, East China University of Science and Technology, Shanghai 200237, China;
2. Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

Received:2017-02-25 Online:2017-07-08 Published:2013-10-18
Supported by:
National Natural Science Foundation of China (No.21375038).

摘要/Abstract

摘要：

绕轴旋转180°能与自身重合的C₂对称型手性化合物在手性催化和手性分离领域有重要应用。以L-脯氨酸苯基酰胺衍生物为手性源，合成了一类新型的C₂对称型手性固定相，并进行了手性色谱拆分评价。与单侧链取代的刷型固定相进行对比，C₂对称型手性固定相对所评价的31种酸性、中性和碱性分析物表现出更好的手性选择性。考察了固定相末端苯环上的取代基团对手性拆分的影响，综合来看，苯环上无取代基的C₂对称型手性固定相的分离性能最优。对某些手性对映体，C₂对称型手性固定相的分离因子随温度的增高而呈现异常增大的现象，表明了其有别于单侧链取代的固定相的分离机理。该类新型手性固定相的提出对进一步丰富刷型手性固定相的种类和拓展其应用具有重要意义。

关键词: C₂对称, 对映体分离, 脯氨酸衍生物, 手性固定相

Abstract:

C₂ symmetric chiral compounds overlap themselves when rotating with an axis of 180° with an axis and have important applications in chiral catalysis and chiral separation fields. A novel C₂ symmetric stationary phase based on phenyl substituted L-proline derivatives was prepared and compared with the similar stationary phase based on mono-substituted brush-type stationary phase. The C₂ symmetric stationary phase showed higher enantiodiscrimination capability than the mono-substituted stationary phase for 31 acidic, neutral and alkaline analytes. The influence of the substitution groups on the terminal phenyl moiety on enantioselectivity was investigated. In summary, the best separation capability was achieved by the stationary phase with none substitution on the endmost phenyl ring. An unusual thermodynamic behavior of the enantioseparation property was observed on the C₂ symmetric stationary phase for some analytes, which showed the different separation mechanism comparing with the corresponding mono-substituted stationary phase. The appearance of this novel chiral stationary phase has an important significance in enriching the type of brush-type stationary phases and widening their applications.

Key words: C₂ symmetric, chiral stationary phase (CSP), enantiomer separation, proline derivatives

中图分类号:

O658

陈龙, 程玲平, 何珊珊, 何云超, 吴亚玲, 柯燕雄, 梁鑫淼. L-脯氨酸衍生物为手性侧链的新型C₂对称型手性固定相[J]. 色谱, 2017, 35(7): 703-711.

CHEN Long, CHENG Lingping, HE Shanshan, HE Yunchao, WU Yaling, KE Yanxiong, LIANG Xinmiao. New C₂ symmetric chiral stationary phases based on L-proline derivatives as chains[J]. Chinese Journal of Chromatography, 2017, 35(7): 703-711.

参考文献

[1] Lin X J, Gong R J, Li P, et al. Chinese Journal of Chromatography, 2014, 32(8):880林小建, 龚如金, 李平, 等. 色谱, 2014, 32(8):880
[2] Chen B P, Li L S, Zhou R D, et al. Chinese Journal of Chromatography, 2014, 32(11):1219程彪平, 李来生, 周仁丹, 等. 色谱, 2014, 32(11):1219
[3] Chen L, Li Y, Nong R Y, et al. Chinese Journal of Analysis Laborator, 2015, 34(12):1365陈玲, 李扬, 农蕊瑜, 等. 分析试验室, 2015, 34(12):1365
[4] Zhang W J, Liang L, Li H. Fine Chemicals, 2012, 29(3):272章文军, 梁莉, 李慧. 精细化工, 2012, 29(3):272
[5] Hou J G, Zhou Z Q, Chen L R, et al. Chinese Journal of Chromatography, 1997, 15(3):206侯经国, 周志强, 陈立仁, 等. 色谱, 1997, 15(3):206
[6] Zheng W L, Song H, Liang Y M, et al. Chinese Journal of Chromatography, 2003, 21(3):239郑文丽, 宋航, 梁彦明, 等. 色谱, 2003, 21(3):239
[7] Yu J J, Lee J M, Ryoo J J. Chirality, 2016, 28:276
[8] Wu H B, Ji S Y, Yang B, et al. J Sep Sci, 2012, 35:351
[9] Pirkle W H, Murray P G. J Chromatogr A, 1996, 719:299
[10] Delgado B, Perez E, Santano M C, et al. J Chromatogr A, 2005, 1092:36
[11] Ashtari M, Cann N M. J Chromatogr A, 2015, 1409:89
[12] Zhou H, Long Y D, Huang T B, Chinese Journal of Chromatography, 1997, 15(1):26周华, 龙远德, 黄天宝. 色谱, 1997, 15(1):26
[13] Huang J, Zhang P, Chen H, et al. Anal Chem, 2005, 77(10):3301
[14] Huang J, Chen H, Li T. J Chromatogr A, 2006, 1113:109
[15] Huang J, Chen H, Zhang P, et al. J Chromatogr A, 2006, 1109:307
[16] Wu H B, Song G J, Liang X M, et al. Chin J Chem, 2012, 30:2791
[17] Wu H B, Song G J, Wang D Q, et al. J Chromatogr A, 2013, 1298:152
[18] Wu H B, Wang D Q, Song G J, et al. J Sep Sci, 2014, 37:934
[19] Kagan H B, Dang T P. J Am Chem Soc, 1972, 94:29
[20] Jin Y, Zhang T Y, Wang L M, et al. Chemical Reagents, 2013, 35(9):789金瑛, 张天一, 王黎明, 等. 化学试剂, 2013, 35(9):789
[21] Ma M L, Zhang Y Y, Yang J, et al. Journal of Xihua University, 2013, 32(1):7马梦林, 张园园, 杨静, 等. 西华大学学报, 2013, 32(1):7
[22] Cai W S, Feng C L, Ma X Y, et al. Electrochim Acta, 2015, 169:424
[23] Mikes F, Boshart G. J Chromatogr A, 1978, 149:455
[24] Feibush B, Figueroa A, Charles R, et al. J Am Chem Soc, 1986, 108(12):3310
[25] Shinbo T, Yamaguchi T, Nishimura K, et al. J Chromatogr A, 1987, 405:145
[26] Tichy M, Holnaova J, Zavada J. J Chromatogr A, 1994, 667:11
[27] Gasparrini F, Misiti D, Villani C. J Org Chem, 1995, 60(14):4314
[28] Yu J, Ryoo D, Lee J, et al. Chirality, 2016, 28:186
[29] Kelly S E, LaCour T G. Synth Commun, 1992, 22(6):859
[30] Tu S J, Fang F, Zhu S L, et al. Synlett, 2004, 3:537
[31] Zhang H, Guo D L, Deng Y W, et al. Chinese Journal of Analytical Chemistry, 2013, 41(8):1209张华, 郭丹丽, 邓毓文, 等. 分析化学, 2013, 41(8):1209
[32] Yao B, Zhan F, Yu G, et al. J Chromatogr A, 2009, 1216:5429
[33] Jonsson S, Schon A, Isaksson R, et al. Chirality, 1992, 4:505
[34] Fornstedt T, Sajonz P, Guiochon G. J Am Chem Soc, 1997, 119(6):1252

L-脯氨酸衍生物为手性侧链的新型C₂对称型手性固定相

New C₂ symmetric chiral stationary phases based on L-proline derivatives as chains

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