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<p>Selective fluorine substitution(s) in polyfluoroarenes with other functionalities can effectively tune their properties. However, diverse C–F functionalizations of polyfluoroarenes with varying fluorine numbers and substitution patterns remain a formidable challenge. Here we describe a distinct radical approach employing reactivity-tunable pyridine-boryl radicals as link-and-lose mediators for C–F transformations of various hexa- to difluoroarenes. The reaction starts with pyridine-boryl radical attack to a polyfluoroarene (‘link’), which facilitates a distinct heterolytic cleavage of the <i>ipso</i> C–F bond to generate a unique polyfluoroaryl radical cation intermediate under non-reductive conditions. Capturing this intermediate by diverse coupling partners with concurrent departure of boron moiety (‘lose’) enables hydro- and deuterodefluorination, as well as defluorinative arylation with arenes and alkylation with alkenes/alkanes. This process is applicable to functionalize the second, third and even fourth C–F bond, enabling vast structural diversity. Time-resolved electron paramagnetic resonance spectroscopy provides direct evidence of key intermediates involved, validating the distinct radical cascade.</p><p></p>

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Diverse radical C–F functionalizations of hexa- to difluoroarenes using boryl radicals as link-and-lose mediators

  • 期刊论文

  • 发表日期：

    2026年4月22日

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  • Tian Ye,
  • Fang-Song Zhang,
  • Zhe-Yuan Xu,
  • Sheng-Qi Zhou,
  • Yee Lin Phang,
  • Zhi-Qiang Ding,
  • Feng-Lian Zhang,
  • Wen-Chao Yang,
  • Zhong-Ping Cai,
  • Yuan Peng,
  • Bing-Yi Zhou,
  • Wei-Qun Suo,
  • Xingwei Guo,
  • Yao Fu,
  • Yi-Feng Wang

摘要

Selective fluorine substitution(s) in polyfluoroarenes with other functionalities can effectively tune their properties. However, diverse C–F functionalizations of polyfluoroarenes with varying fluorine numbers and substitution patterns remain a formidable challenge. Here we describe a distinct radical approach employing reactivity-tunable pyridine-boryl radicals as link-and-lose mediators for C–F transformations of various hexa- to difluoroarenes. The reaction starts with pyridine-boryl radical attack to a polyfluoroarene (‘link’), which facilitates a distinct heterolytic cleavage of the ipso C–F bond to generate a unique polyfluoroaryl radical cation intermediate under non-reductive conditions. Capturing this intermediate by diverse coupling partners with concurrent departure of boron moiety (‘lose’) enables hydro- and deuterodefluorination, as well as defluorinative arylation with arenes and alkylation with alkenes/alkanes. This process is applicable to functionalize the second, third and even fourth C–F bond, enabling vast structural diversity. Time-resolved electron paramagnetic resonance spectroscopy provides direct evidence of key intermediates involved, validating the distinct radical cascade.