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有机化学
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有机化学 ›› 2009, Vol. 29 ›› Issue (08): 1282-1286. 上一篇    下一篇

研究简报

BPB-Ni(II)-Ala复合物法不对称合成双-α-甲基氨基酸

叶玲娅; 武红丽; 张小龙; 周佳栋 ; 曹 飞*; 韦 萍   

  1. (南京工业大学制药与生命科学学院 材料化学工程国家重点实验室 南京 210009)
  • 收稿日期:2008-07-05 修回日期:2008-12-29 发布日期:2009-08-30
  • 通讯作者: 曹 飞

Asymmetric Synthesis of Bis(α-methylamino acid) via a BPB-Ni(II)-Ala Complex

Ye , Lingya; Wu, Hongli; Zhang, Xiaolong ; Zhou, Jiadong; Cao, Fei*; Wei, Ping

  

  1. (State Key Laboratory of Materials-Oriented Chemical Engineering, College of Life Science and Pharmaceutical Engineering, Nanjing University of Technology, Nanjing 210009)
  • Received:2008-07-05 Revised:2008-12-29 Published:2009-08-30
  • Contact: Cao, Fei

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被引次数

1

以2-N-(N’-苄基脯氨酰)-氨基二苯甲酮-镍(II)-丙基酸复合物为手性助剂, 与不同碳链长度的二溴烷烃反应制备 双-α-甲基氨基酸. 其中, BPB-Ni(II)-Ala复合物与1,3-二溴丙烷发生取代-消除反应后生成烯丙基取代复合物中间体, 产率高达90%, 水解生成2-甲基-2-氨基-4-烯-戊酸; 与1,4-二溴丁烷、1,5-二溴戊烷、1,6-二溴己烷可以实现双取代反应, 但所得的主要产物为单取代的BPB-Ni(II)-Ala复合物, 双-α-甲基氨基酸复合物中间体收率分别为38%, 36%, 45%, 经过水解后生成相应的双-α-甲基氨基酸, 分别为2,7-二氨基-2,7-二甲基辛二酸、2,8-二氨基-2,8-二甲基壬二酸、2,9-二氨基-2,9-二甲基癸二酸. 手性助剂2-N-(N’-苄基脯氨酰)-氨基二苯甲酮的回收率可高达95%.

关键词: 双-α-甲基氨基酸, BPB-Ni(II)-Ala复合物, 双烷基化, 手性助剂

Several bis(α-methylamino acid)s were synthesized by using alanine-Ni-2[N’-(N-benzylprolyl)- amino]benzophenone [BPB-Ni(II)-Ala] as chiral auxiliary with α,ω-dibromoalkane. The substitution reaction with different carbon chain length of α,ω-dibromoalkanes showed the various results. For 1,3-dibromopropane with BPB-Ni(II)-Ala complex, the mono-alkylation and elimination reaction occurred sequentially, then allylic substitution of BPB-Ni(II)-Ala complex was obtained; while 1,4-dibromobutane, 1,5-dibromopentane and 1,6-dibromohexane were used, bis(α-methylamino acid) dimerization complexes were formed after the mono-alkylation reaction. The yields of the dimerzation complex intermediate products were 38%, 36% and 45%. Then 2,7-diamino-2,7-dimethyloctanedioic acid, 2,8-diamino-2,8-dimethyl-nonanedioic acid, 2,9- diamino-2,9-dimethyldecanedioic acid were obtained by hydroyzing the corresponding bis(α-methylamino acid) complexes. The reaction of BPB-Ni(II)-Ala with 1,3-dibromopropane yielded an S-2-amino-2- methyl-4-pentenoic acid complex, which was then hydrolyzed to S-2-amino-2-methyl-4-pentenoic acid. Chiral auxiliary BPB was recovered in a 95% yield.

Key words: BPB-Ni(II)-Ala complex, chiral auxiliary, dialkylati, bis(α-methylamino acid)