用于芳香胺和醇NMR对映体检测的松香基膦试剂的合成有机化学.pdfVIP

DOI: 10.6023/cjoc1201061 研究论文 有机化学 Chinese Journal of Organic Chemistry ARTICLE 用于芳香胺和醇NMR 对映体检测的松香基膦试剂的合成 吴 强 姚贵阳 朱永涛 王恒山* 何春欢 潘英明* (广西师范大学化学化工学院 药用资源化学与药物分子工程重点实验室 桂林 541004) 摘要 以松香为原料通过三步反应高产率合成手性二醇 3 和手性单醇 6, 将它们用作手性助剂现场制备有机膦衍生试 剂, 分别对单官能团手性底物(单胺、单醇)和双官能团底物(双胺、双醇及氨基醇)进行衍生, 通过 31P NMR 测定, 其芳 基底物非对映体衍生物的膦化学位移差异值(Δδp)在 3.08～0.10 之间, 均能够在测定条件下实现对映体峰的基线分离. 用于 α-萘乙胺和 1,1-联二萘酚(BINOL)样品对映体过量值测定, 相对误差小于±2%. 关键词 31P NMR; 对映体过量检测; 松香基膦试剂 Synthesis of Rosin Derived Chiral Derivatizing Agents for 31P NMR Assays of Amine or Alcohol and Amino Alcohol Enantiomers Wu, Qiang Yao, Guiyang Zhu, Yongtao Wang, Hengshan* He, Chunhuan Pan, Yingming* (Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry Chemical Engineering, Guangxi Normal University, Guilin 541004) Abstract Chiral alcohols 3 and 6 were synthesized in optically pure forms from easily available rosin acid in short-steps. A comprehensive protocol for the enantiomeric excess assays of mono- or di-functional-grouped chiral secondary amine or al- cohol has been established by using them as chiral auxiliary for chiral phosphorus derivatizing reagents (CPDA) in 31P NMR tests. Chemical shift difference (Δδ ) values ranging from 3.08 to 0.10 between two diastereoisomers of the CPDAs and the p aryl substrates were obtained. The enantiomeric excess of 1-(1-naphthyl)ethylamine and 1,1-bi(2-naphthol) is determined using our CPDA, and the results showed that the