Creation of super-efficient chiral selector and practical use of chemically bonded type chiral column

超高效手性选择剂的研制及化学键合型手性柱的实用化

基本信息

批准号：
15350081
负责人：
HIROSE Keiji
金额：
$ 4.29万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2004
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15350081/
关键词：
Chromatography Chiral recognition Chiral selector Optical activity Chiral Separation Crown Ether Amine Optical Resolution キラルセレクター

项目摘要

We have prepared chiral stationary phases 1 having anisole type pseudo-18-crown-6 ether as selector, and found high separation ability of chiral amino compound. This CSP was succeeded to put to practical use. In order to investigate the effect of structure of chiral moiety and functional group placed in the crown cavity on enantioselectivity, chiral column (2,3) having phenolic psoudo-18-crown-6 ethers as selectors were synthesized. The enantioselectivity of the selectors having 1-phenyl-1,2-cydohexanediol (4,5),3,5-dimethylphenyl derivative (6),4-tryfluoromethylphenyl derivative (7), and 1-naphtyl derivative (8) were investigated. Corresponding chiral selectors (9,10,11,12) were derived to CSPs (1,13,14,15) and chiral column for chromatography were prepared. In addition, chiral selectors for secondary amines were designed and synthesized. Chiral crown ether 11 was applied for chiral sift reagent with lanthanide compound.Chromatographic performance of chemically bonded type CSP 13 having a relatively bulky chiral 1-phenyl-1,2-cydohexanediol unit was tested. Using normal phase chromatographic conditions, CSP 13 exhibited short retention times and good resolution of the enantiomers of various amino compounds including amino acids, amino alcohols, and hydrophobic amino compounds. The separation of relatively bulky amino compounds was better on CSP 1, whereas small amino compounds were separated better on CSP 13 Overall, considerable improvements in the enantiomer separation was achieved for many amino compounds on CSP 13 compared to CSP 1. CSP 13 is not always superior to CSP 1. The two CSPs are complementary with each other in terms of chiral recognition. CSP 13 and CSP 1 have little restriction in mobile phases, additives, and analytes because of chemically bonded nature, so that both phases have wide applicability for enantiomer separation.

我们制备了以苯甲醚型准18冠6醚为选择剂的手性固定相1，发现手性氨基化合物具有较高的分离能力。该CSP已成功投入实际应用。为了研究冠腔中手性部分的结构和官能团对对映选择性的影响，合成了以酚类拟18-冠-6醚为选择剂的手性柱(2,3)。研究了具有1-苯基-1,2-环己二醇(4,5)、3,5-二甲基苯基衍生物(6)、4-三氟甲基苯基衍生物(7)和1-萘基衍生物(8)的选择剂的对映选择性。衍生出相应的手性选择剂（9、10、11、12）为CSP（1、13、14、15），并制备了色谱手性柱。此外，还设计并合成了仲胺的手性选择剂。将手性冠醚11应用于镧系化合物的手性筛选试剂。测试了具有较大手性1-苯基-1,2-环己二醇单元的化学键合型CSP 13的色谱性能。使用正相色谱条件，CSP 13 对各种氨基化合物（包括氨基酸、氨基醇和疏水性氨基化合物）的对映体表现出较短的保留时间和良好的分离度。相对较大的氨基化合物在 CSP 1 上的分离效果更好，而小氨基化合物在 CSP 13 上的分离效果更好总体而言，与 CSP 1 相比，CSP 13 上的许多氨基化合物在对映体分离方面取得了相当大的改进。CSP 13 并不总是如此优于CSP 1。两种CSP在手性识别方面具有互补性。由于化学键合性质，CSP 13 和 CSP 1 对流动相、添加剂和分析物几乎没有限制，因此两种相都具有广泛的对映体分离适用性。