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<p>Designing and developing synthetically useful biocatalytic reactions that operate through unconventional mechanisms represent a central challenge in modern biocatalysis research. By coupling photoredox catalysis and metalloenzyme catalysis, here we harness cooperative photometallobiocatalysis to merge enzymatically generated, open-shell iron carbenoids with reactive radical intermediates formed via excited-state chemistry. This strategy expands the scope of intermolecular radical C–C coupling reactions with excellent enantio- and diastereoselectivities. Central to the successful implementation of this design is the directed evolution of a small metalloprotein catalyst, derived from a thermophilic cytochrome <i>c</i>, to achieve challenging stereocontrol in radical C–C coupling via an outer-sphere mechanism. These photobiocatalytic, formal metal carbenoid–radical coupling reactions advance a distinct mode of stereoselective outer-sphere metal carbenoid chemistry, providing a powerful strategy to design and evolve biocatalytic C–C bond-forming reactions through otherwise challenging intermolecular asymmetric radical couplings.</p><p></p>

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Stereoselective photometallobiocatalytic cross-coupling of organoboron reagents and diazo compounds via an outer-sphere mechanism

  • 期刊论文

  • 发表日期：

    2026年4月29日

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  • Huanan Wang,
  • Binh Khanh Mai,
  • Chongtao Li,
  • Xiao-Wang Chen,
  • Rachel Weiss,
  • Bryan Kudisch,
  • Peng Liu,
  • Yang Yang

摘要

Designing and developing synthetically useful biocatalytic reactions that operate through unconventional mechanisms represent a central challenge in modern biocatalysis research. By coupling photoredox catalysis and metalloenzyme catalysis, here we harness cooperative photometallobiocatalysis to merge enzymatically generated, open-shell iron carbenoids with reactive radical intermediates formed via excited-state chemistry. This strategy expands the scope of intermolecular radical C–C coupling reactions with excellent enantio- and diastereoselectivities. Central to the successful implementation of this design is the directed evolution of a small metalloprotein catalyst, derived from a thermophilic cytochrome c, to achieve challenging stereocontrol in radical C–C coupling via an outer-sphere mechanism. These photobiocatalytic, formal metal carbenoid–radical coupling reactions advance a distinct mode of stereoselective outer-sphere metal carbenoid chemistry, providing a powerful strategy to design and evolve biocatalytic C–C bond-forming reactions through otherwise challenging intermolecular asymmetric radical couplings.