基于光诱导单电子转移反应历程合成醚-聚N-苄基甘氨酸肽环化物有机化学.pdfVIP

DOI: 10.6023/cjoc201302015 研究论文 有机化学 Chinese Journal of Organic Chemistry ARTICLE 基于光诱导单电子转移反应历程合成醚-聚N-苄基甘氨酸肽环化物 粱波颖 金英学 于沙沙 曲凤玉 谭广慧* (哈尔滨师范大学化学化工学院 哈尔滨 150025) 摘要 研究了以邻苯二甲酰亚胺为电子受体, 以末端三甲基硅烷基的醚-聚 N -苄基甘氨酸肽链为电子给体的化合物 5a～5f 的光反应, 发展了新的合成环肽类化合物的方法. 末端三甲基硅烷基的醚-聚 N-苄基甘氨酸肽链——邻苯二甲 酰亚胺5a～5f 在甲醇溶剂中进行光反应, 经连续的单电子转移(SET)历程有效地合成了环肽类化合物6a～6f. 所合成的 环肽类化合物的结构经核磁共振谱、高分辨质谱、X 光晶体衍射所确定. 关键词 单电子转移(SET); 光环化; 环肽; 邻苯二甲酰亚胺; N-三甲基硅烷基甲基肽电子给体 Synthesis of Cyclic Ether-N-Benzyl Glycine Polypeptides Based on Single Electron Transfer-Promoted Photocyclization Processes Liang, Boying Jin, Yingxue Yu, Shasha Qu, Fengyu Tan, Guanghui* (College of Chemistry Chemical Engineering, Harbin Normal University, Harbin 150025) Abstract Exploratory photochemical studies on trimethylsilyl-terminated phthalimide-ether-N-benzylpolyglycines in which phthalimides worked as light absorbance acceptors and ether-N-(trimethylsilyl)methylamides served as electron donor centers have been conducted, leading to the development of new synthetic methodology to construct cyclic polypeptide mimetics. It was found that irradiation on trimethylsilyl-terminated phthalimide-ether-poly-N-benzylglycine 5a～5f in methanol led to efficient generation of cyclic peptide products 6a～6f, which may be through sequential single electron transfer (SET) path- way. The structures of these cyclic peptide products were determined by NMR and HRMS spectroscopy as well as fully char- acterized by X-ray crystallography. Keywords single electron transfer (SET); photoyclization; cyclic peptide; phthalimide; N-trimethylsilylmethyl peptide elec- t