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<p>Direct functionalization of abundant C(<i>sp</i><sup>3</sup>)–H bonds is highly attractive. Photobiocatalysis offers promise for expanding enzyme reactivity but has been limited to the use of preactivated radical precursors. Key challenges for C(<i>sp</i><sup>3</sup>)–H bond activation include the lack of robust activation modes for the inert bonds under biocatalytic conditions and controlling the reactivity and stereochemistry of prochiral radicals. Here we report a triple activation strategy enabling photobiocatalytic C(<i>sp</i><sup>3</sup>)–H bond acylation with aldehydes. By combining hydrogen-atom transfer for prochiral radical formation, organic-dye-modulated single-electron transfer and an engineered thiamine-dependent enzyme, we describe a radical acyl transferase for functionalizing C(<i>sp</i><sup>3</sup>)–H bonds. This robust radical enzymatic system achieves benzylic C(<i>sp</i><sup>3</sup>)–H and aldehyde C(<i>sp</i><sup>2</sup>)–H oxidative coupling in an enantioselective manner (up to 97% e.e.).</p><p></p>

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Photobiocatalytic benzylic C–H acylation enabled by the synergy of a thiamine-dependent enzyme, an organophotocatalyst and hydrogen-atom transfer

  • 期刊论文

  • 发表日期：

    2025年8月19日

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  • Xichao Peng,
  • Jianqiang Feng,
  • Fulu Liu,
  • Wen-Zheng Xie,
  • Hailong Sun,
  • Yuanyuan Xu,
  • Yang Ming,
  • Zhongqiu Xing,
  • Yu Zheng,
  • Binju Wang,
  • Yi-Tao Long,
  • Xiaoqiang Huang

摘要

Direct functionalization of abundant C(sp3)–H bonds is highly attractive. Photobiocatalysis offers promise for expanding enzyme reactivity but has been limited to the use of preactivated radical precursors. Key challenges for C(sp3)–H bond activation include the lack of robust activation modes for the inert bonds under biocatalytic conditions and controlling the reactivity and stereochemistry of prochiral radicals. Here we report a triple activation strategy enabling photobiocatalytic C(sp3)–H bond acylation with aldehydes. By combining hydrogen-atom transfer for prochiral radical formation, organic-dye-modulated single-electron transfer and an engineered thiamine-dependent enzyme, we describe a radical acyl transferase for functionalizing C(sp3)–H bonds. This robust radical enzymatic system achieves benzylic C(sp3)–H and aldehyde C(sp2)–H oxidative coupling in an enantioselective manner (up to 97% e.e.).