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<p>Radical C(<i>sp</i><sup>3</sup>)–C(<i>sp</i><sup>3</sup>) bond formation has emerged as a promising strategy for constructing molecules rich in C(<i>sp</i><sup>3</sup>)–stereocentres. However, achieving chemo- and enantioselective recombination of two prochiral alkyl radicals remains a substantial challenge. Here we synergistically repurpose a thiamine-dependent benzoylformate decarboxylase (<i>Pp</i>BFD) with a photoinduced radical process, unlocking unnatural photobiocatalytic C(<i>sp</i><sup>3</sup>)–C(<i>sp</i><sup>3</sup>) bond formation. This system converts simple cinnamyl aldehydes into enantioenriched carboxylic acids bearing valuable β-, or β,γ-C(<i>sp</i><sup>3</sup>)–stereocentres, a new-to-nature transformation that is difficult to achieve with conventional methods. Through directed evolution, we precisely control alkyl radicals to achieve stereoselective C(<i>sp</i><sup>3</sup>)–C(<i>sp</i><sup>3</sup>) bond formation (38 examples, up to 96% e.e. and up to 91:9 d.r.). This work demonstrates that the reshaping of a different class of thiamine-dependent enzymes can expand the repertoire of radical biocatalysis.</p><p></p>

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Enantioselective C(sp3)–C(sp3) bond formation by synergistic thiamine-dependent radical biocatalysis and photoredox catalysis

  • 期刊论文

  • 发表日期：

    2026年4月2日

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  • Jianlin Chun,
  • Yuyan Bao,
  • Qiaoyu Zhang,
  • Xueli Hou,
  • Zhouping Wu,
  • Hailong Sun,
  • Zhongqiu Xing,
  • Bin Chen,
  • Zihan Zhang,
  • Yue Zhao,
  • Jiahai Zhou,
  • Binju Wang,
  • Xiaoqiang Huang

摘要

Radical C(sp3)–C(sp3) bond formation has emerged as a promising strategy for constructing molecules rich in C(sp3)–stereocentres. However, achieving chemo- and enantioselective recombination of two prochiral alkyl radicals remains a substantial challenge. Here we synergistically repurpose a thiamine-dependent benzoylformate decarboxylase (PpBFD) with a photoinduced radical process, unlocking unnatural photobiocatalytic C(sp3)–C(sp3) bond formation. This system converts simple cinnamyl aldehydes into enantioenriched carboxylic acids bearing valuable β-, or β,γ-C(sp3)–stereocentres, a new-to-nature transformation that is difficult to achieve with conventional methods. Through directed evolution, we precisely control alkyl radicals to achieve stereoselective C(sp3)–C(sp3) bond formation (38 examples, up to 96% e.e. and up to 91:9 d.r.). This work demonstrates that the reshaping of a different class of thiamine-dependent enzymes can expand the repertoire of radical biocatalysis.