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有机化学
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有机化学 ›› 2005, Vol. 25 ›› Issue (12): 1615-1618. 上一篇    下一篇

研究简报

新型双烯丙基化手性二胺的合成

王辉，裴伟伟*，王羿   

  1. (北京大学化学与分子工程学院 生物有机与分子工程教育部重点实验室 北京 100871)
  • 收稿日期:2005-02-21 修回日期:2005-06-29 发布日期:2005-11-30
  • 通讯作者: 裴伟伟

Synthesis of Novel Chiral Diallylic Diamine

WANG Hui, PEI Wei-Wei*, WANG Yi   

  1. (Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education of China,
    College of Chemistry and Molecular Engineering, Peking University, Beijing 100871)
  • Received:2005-02-21 Revised:2005-06-29 Published:2005-11-30
  • Contact: PEI Wei-Wei

PDF

2036

被引次数

19

通过烯丙基溴化锌对手性亚胺的两次不对称加成, 合成了光活性的双烯丙基化的新型手性二胺. 首先经N-Boc保护和Dess-Martin氧化制得了光活性的(S)-N-Boc-3-苯基-2-氨基丙醛. (S)-N-Boc-3-苯基-2-氨基丙醛与(S)-缬氨基酸甲酯缩合生成手性亚胺, 在七水合三氯化铈(CeC13•7H2O)催化以及底物的手性诱导作用下, 该手性亚胺与烯丙基溴化锌经不对称加成反应合成了高光活性的单烯丙基化手性胺. 该手性胺与2-噻吩甲醛缩合生成新的手性亚胺, 再次通过不对称烯丙基加成反应合成了含有四个手性中心的高光学纯的双烯丙基化手性二胺. 目标化合物和关键中间体的结构均被1H NMR, 13C NMR及MS确证.

关键词: 手性α-氨基醛, 手性二胺, 亚胺, 烯丙基溴, 不对称加成

A novel chiral diallylic diamine has been synthesized through double addition of allyl zinc bromide to chiral imines in this contribution. Firstly, (S)-N-Boc-2-amino-3-phenylpropanal was prepared through N-Boc protection and Dess-Martin oxidation. Then, it was condensed with (S)-valine methyl ester to form a chiral imine, which was reacted with allyl zinc bromide in the presence of CeC13•7H2O to afford the corresponding chiral homoallylic amine with high optical activity. After removing Boc group, the newly formed chiral homoallylic amine was condensed with 2-thiophenecarboxaldehyde to provide a novel chiral imine with high optical purity. The following asymmetric addition of allyl zinc bromide to the novel chiral imine provided the target compound. The structure and the purity of desired compound and the key intermediates were demonstrated by 1H NMR, 13C NMR and MS spectra.

Key words: imine, chiral diamine, allyl bromide, asymmetric addition, chiral α-amino aldehyde