光诱导单电子转移反应合成氮杂环脯氨酸肽  

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

作　　者：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] 

机构地区：[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

出　　处：《有机化学》2011年第4期480-485,共6页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.20972036);黑龙江省自然科学基金(No.B200913);黑龙江省教育厅海外学人科研基金(No 1152hq23);山东省自然科学基金(No.Y2008B49)资助项目

摘　　要：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.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,co-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.

关 键 词：光诱导 单电子转移 环肽 区域选择性 

分 类 号：R914[医药卫生—药物化学]