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<p>Radical repositioning, a transformative strategy for activating remote C–C/C–H bonds through the relocation of unpaired electrons, remains unexplored in biological systems. Recent advances in photogenerated nitrogen-centred radicals (NCRs) have enabled radical 1,2- to 1,<i>n</i>-translocations for organic synthesis, but achieving stereochemical control over the repositioned prochiral radicals is challenging. Here we introduce a visible light-promoted, thiamine-dependent radical biocatalytic system that leverages NCR-triggered radical repositioning for the enantioselective acylation of remote C–C/C–H bonds. Synergistic single-electron transfer and thiamine cofactor-mediated biocatalysis enables the generation of NCRs, which translocate to remote carbon-centred radicals via 1,<i>n</i>-hydrogen atom transfer or C–C fragmentation, and facilitates the subsequent radical cross-coupling within the active site, producing diverse chiral nitriles and amides with a remote carbonyl group (43 examples with a δ-, ε-, ζ- or η-position relative to the N atom) in good-to-excellent enantiomeric ratios (up to 99.5:0.5). This strategy couples radical repositioning and enzymes to unlock the selective functionalization of remote C–H/C–C bonds.</p><p></p>

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Photobiocatalytic radical repositioning for enantioselective acylation of remote C–C/C–H bonds

  • 期刊论文

  • 发表日期：

    2025年11月3日

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  • Yang Ming,
  • Zhouping Wu,
  • Yuanyuan Xu,
  • Yao Chen,
  • Zhongqiu Xing,
  • Xichao Peng,
  • Jianlin Chun,
  • Hailong Sun,
  • Jiayu Wu,
  • Yu Zheng,
  • Ling Jiang,
  • Xiaoqiang Huang

摘要

Radical repositioning, a transformative strategy for activating remote C–C/C–H bonds through the relocation of unpaired electrons, remains unexplored in biological systems. Recent advances in photogenerated nitrogen-centred radicals (NCRs) have enabled radical 1,2- to 1,n-translocations for organic synthesis, but achieving stereochemical control over the repositioned prochiral radicals is challenging. Here we introduce a visible light-promoted, thiamine-dependent radical biocatalytic system that leverages NCR-triggered radical repositioning for the enantioselective acylation of remote C–C/C–H bonds. Synergistic single-electron transfer and thiamine cofactor-mediated biocatalysis enables the generation of NCRs, which translocate to remote carbon-centred radicals via 1,n-hydrogen atom transfer or C–C fragmentation, and facilitates the subsequent radical cross-coupling within the active site, producing diverse chiral nitriles and amides with a remote carbonyl group (43 examples with a δ-, ε-, ζ- or η-position relative to the N atom) in good-to-excellent enantiomeric ratios (up to 99.5:0.5). This strategy couples radical repositioning and enzymes to unlock the selective functionalization of remote C–H/C–C bonds.