可见光促进的含色氨酸寡肽与YlideFluor试剂的直接三氟甲基化反应研究  

Visible-Light-Promoted Direct Trifluoromethylation of TryptophanContaining Oligapeptides with YlideFluor

作　　者：刘静 郝健[1] 沈其龙[2] Liu Jing;Hao Jian;Shen Qilong(Department of Chemistry,Shanghai University,Shanghai 200444;Key Laboratory of Organofluorine Chemistry,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032)

机构地区：[1]上海大学化学系,上海200444 [2]中国科学院上海有机化学研究所有机氟化学重点实验室,上海200032

出　　处：《有机化学》2023年第4期1517-1524,共8页Chinese Journal of Organic Chemistry

基　　金：国家重点研发计划(No.2021YFF0701700)资助项目.

摘　　要：发展了一个温和条件下可见光促进的含色氨酸的寡肽与YlideFluor试剂的三氟甲基化反应.初步的机理研究表明在反应过程中1,8-二氮杂二环[5.4.0]十一碳-7-烯(DBU)与YlideFluor试剂之间形成了一个供体-给体复合物,在光照条件下,该复合物被激发后分子中的硫-碳键发生均裂生成三氟甲基自由基,该自由基进攻寡肽的色氨酸吲哚片段的2-位,生成相应的三氟甲基修饰的寡肽.A photosensitizer-free visible-light-promoted method for site-selective trifluoromethylation of tryptophancontaining oligopeptides using YlideFluor as the trifluoromethyl radical source under mild conditions was developed.Mechanistic studies showed that a donor-acceptor between 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU)and YlideFluor is generated.Upon irradiation with blue LEDs,the S-CF3 bond in the adduct undergoes homolytic cleavage to give trifluoromethyl radical,which attacks the electron-rich C-2 position of the indole moiety in the tryptophan-containing oligopeptide.

关 键 词：氟 三氟甲基 色氨酸 寡肽 可见光 

分 类 号：O621.25[理学—有机化学]