有机化学 ›› 2013, Vol. 33 ›› Issue (12): 2545-2550.DOI: 10.6023/cjoc201307007 上一篇    下一篇

研究论文

手性氨基酸衍生物的合成:硅胶促进的取代氮丙啶的开环反应

李小娜, 周宏勇, 张鹏亮, 王家喜   

  1. 河北工业大学绿色化工与高效节能重点实验室 天津 300130
  • 收稿日期:2013-07-05 修回日期:2013-08-10 出版日期:2013-12-25 发布日期:2013-08-16
  • 通讯作者: 王家喜 E-mail:jwang252004@126.com
  • 基金资助:

    河北省自然科学基金(No. 2011202087)资助项目.

Synthesis of Chiral Amino-acids Derivatives:Silica-gel Promoted Ring Opening of Substituted Aziridines

Li Xiaona, Zhou Hongyong, Zhang Pengliang, Wang Jiaxi   

  1. Hebei Univ Technol, Key Lab Green Chem Technol & High Efficient Energy, TianJin 300130
  • Received:2013-07-05 Revised:2013-08-10 Online:2013-12-25 Published:2013-08-16
  • Supported by:

    Project supported by the Natural Science Foundation of Hebei Province (No. 2011202087).

通过硅胶促进的L-氨基酸酯与取代氮丙啶的开环反应合成了一系列手性氨基酸衍生的二胺和三胺化合物,上述开环反应可被超声波加速. 所得化合物的结构经1H NMR,13C NMR,IR,元素分析等手段表征. S-2-(二(2-(4-甲基苯磺酰胺乙基)胺基-3-甲基丁酸甲酯(4c)的结构经X射线单晶衍射进一步确定. L-脯氨酸甲酯(1d)与2-异丙基-N-对甲苯磺酰氮丙啶(5)发生1-3开环反应选择性形成化合物6b.

关键词: 氨基酸, 取代氮丙啶, 开环反应, 固相合成, X射线衍射

Chiral amine is a kind of important chemicals. Several L-amino acid based chiral diamines and triamines were prepared by ring-opening of substituted aziridines with L-amino acid esters in the matrix of silica without solvent. The ring-opening reactions were promoted by silica and accelerated by ultrasound radiation. The L-amino acid esters reacted with substituted aziridine 2 to give diamine 3 at first, then diamine 3 reacted with aziridine 2 again to form triamine 4. Compared with L-amino acid esters 1, compound 3 had a higher activity. (S)-Methyl pyrrolidine-2-carboxylate (1d) reacted with (R)-2-isopropyl-1-tosylaziridine (5) selectively yielding (S)-methyl 1-[(R)-3-methyl-2-(4-methylphenyl sulfonamide)butyl]pyr-rolidine-2-carboxylate (6b) through the ring opening at 1,3-position of aziridine. All obtained compounds were characterized by 1H NMR, 13C NMR, IR and elemental analysis. 4c was analyzed by X-ray diffraction as well.

Key words: amino acids, substituted aziridine, ring opening, solid phase synthesis, X-ray diffraction