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2023 , Vol. 43 >Issue 4: 1517 - 1524

DOI: https://doi.org/10.6023/cjoc202209018

研究论文

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

  • 刘静 ,
  • 郝健 ,
  • 沈其龙
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  • a 上海大学化学系 上海 200444
    b 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

收稿日期: 2022-09-14

  修回日期: 2022-11-14

  网络出版日期: 2022-11-22

基金资助

国家重点研发计划(2021YFF0701700)

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Visible-Light-Promoted Direct Trifluoromethylation of Tryptophan-Containing Oligapeptides with YlideFluor

  • Jing Liu ,
  • Jian Hao ,
  • Qilong Shen
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  • a Department of Chemistry, Shanghai University, Shanghai 200444
    b Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
* Corresponding author. ;

Received date: 2022-09-14

  Revised date: 2022-11-14

  Online published: 2022-11-22

Supported by

National Key Research and Development Program of China(2021YFF0701700)

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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.

关键词： 氟; 三氟甲基; 色氨酸; 寡肽; 可见光

本文引用格式

刘静 , 郝健 , 沈其龙 . 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[J]. 有机化学, 2023 , 43(4) : 1517 -1524 . DOI: 10.6023/cjoc202209018

Abstract

A photosensitizer-free visible-light-promoted method for site-selective trifluoromethylation of tryptophan- containing 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.

Key words： fluorine; trifluoromethyl; tryptophan; oligapeptide; visible light

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