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<p>Integrating metal-catalysed transformations into enzymes is a key objective in biocatalysis. This study uses a photoinduced ligand-to-metal charge transfer strategy to enable abiotic cross-coupling reactions in metalloenzymes. By tailoring the primary coordination sphere to establish a 2-histidine metal-binding site and replacing the iron centre with nickel, the ethylene-forming enzyme from <i>Pseudomonas savastanoi</i> (<i>Ps</i>EFE) was activated for nickel-catalysed C(<i>sp</i><sup>2</sup>)‒S cross-coupling between aryl bromides and thiols. Directed evolution of <i>Ps</i>EFE produced variants capable of generating a range of thioether products in up to 98% yield and 530 total turnover numbers. Mechanistic investigations suggest that this photoenzymatic reaction involves a Ni(II)/Ni(I)/Ni(III) catalytic cycle with generation of a reactive Ni(I) species and thiyl radical via photoinduced ligand-to-metal charge transfer. We anticipate that these findings will inspire further exploration of integrating abiotic cross-coupling transformations into enzymatic catalysis.</p><p></p>

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Engineering non-haem enzymes for nickel-catalysed C(sp2)‒S coupling via ligand-to-metal charge transfer photocatalysis

  • 期刊论文

  • 发表日期：

    2026年2月27日

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  • Xiuze Wang,
  • Xianhai Tian,
  • Xiahe Chen,
  • Guoxiong Xu,
  • Jared C. Paris,
  • Yuqi Song,
  • Yuxuan Su,
  • James G. Zhang,
  • Xin Hong,
  • Marc Garcia-Borràs,
  • Arthur E. Bragg,
  • Yisong Guo,
  • Yunfang Yang,
  • Xiongyi Huang

摘要

Integrating metal-catalysed transformations into enzymes is a key objective in biocatalysis. This study uses a photoinduced ligand-to-metal charge transfer strategy to enable abiotic cross-coupling reactions in metalloenzymes. By tailoring the primary coordination sphere to establish a 2-histidine metal-binding site and replacing the iron centre with nickel, the ethylene-forming enzyme from Pseudomonas savastanoi (PsEFE) was activated for nickel-catalysed C(sp2)‒S cross-coupling between aryl bromides and thiols. Directed evolution of PsEFE produced variants capable of generating a range of thioether products in up to 98% yield and 530 total turnover numbers. Mechanistic investigations suggest that this photoenzymatic reaction involves a Ni(II)/Ni(I)/Ni(III) catalytic cycle with generation of a reactive Ni(I) species and thiyl radical via photoinduced ligand-to-metal charge transfer. We anticipate that these findings will inspire further exploration of integrating abiotic cross-coupling transformations into enzymatic catalysis.