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有机化学
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有机化学 ›› 2011, Vol. 31 ›› Issue (04): 480-485. 上一篇    下一篇

研究论文

光诱导单电子转移反应合成氮杂环脯氨酸肽

刘岩1，谭广慧1，魏树权1，曲凤玉1，王进军2，王天赤1，岳群峰1，金英学*,1   

  1. (1哈尔滨师范大学化学化工学院 哈尔滨 150025)
    (2烟台大学化学生物理工学院 烟台 264005)
  • 收稿日期:2010-04-14 修回日期:2010-07-07 发布日期:2010-11-23
  • 通讯作者: 金英学 E-mail:yenghak@hrbnu.edu.cn
  • 基金资助:

    多供电子体-酰亚胺体系电子转移光反应效率及大环化合物的合成与荧光感应性能研究

Synthesis of Heteronitrogen Cyclic Proline Peptides by Photoinduced Single Electron Transfer Reactions

Liu Yan1 Tan Guanghui1 Wei Shuquan1 Qu Fengyu1 Wang Jinjun2 Wang Tianchi1 Yue Qunfeng1 Jin Yingxue*,1   

  1. (1 College of Chemistry & Engineering, Harbin Normal University, Harbin 150025)
    (2 College of Chemistry & Biology, Yantai University, Yantai 264005)
  • Received:2010-04-14 Revised:2010-07-07 Published:2010-11-23

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1153

被引次数

6 | 3

以脯氨酸为起始原料合成了四个光反应底物N-(末端三甲基硅苄基脯氨酸肽链)邻苯二甲酰亚胺(4), 并在甲醇溶剂中进行了光反应. 结果表明, 4的光致激发态分子内发生单电子转移反应, 生成双离子自由基8, 电子沿着化学键在给电子杂原子间转移, 达到共振平衡, 离去基团离去使平衡向末端杂原子方向移动, 高选择性地生成分子内端位双自由基9, 自由基偶合生成标题化合物5. 此反应产率较好, 区域选择性高, 所有新化合物结构均经NMR和质谱验证.

关键词: 光诱导, 单电子转移, 环肽, 区域选择性

Four photoreactants N-(amidosilane terminated polyproline peptide chain) phthalimide (4a～4d) were synthesized by using proline as the starting material, and were irradiated in methanol. The results confirmed that photoinduced excited states of 4a～4d were observed to promote formation of zwitterion biradical (8) by single electron transfer in the molecule. In this process, intrachain SET (ISET) happened among electron donors and an equation of resonant appeared. Intermolecular biradicals (9) were formed in high selectivity by shuck off the leaving group of 1,ω-zwitterionic biradicals (8). The biradicals 9 copulated to give the title compound cyclopeptides 5 in high yield and high regioselectivity. Structures of all compounds were characterized by FAB-MS, NMR techniques.

Key words: photoinduced, single electro transfer, cyclic peptide, regioselectivity