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<p>Asymmetric addition to unsaturated double bonds provides an efficient strategy for the synthesis of optically active molecules. Despite advances over the past decades, achieving highly enantioselective transformations of purely alkyl-substituted 1,1-dialkylethenes has remained a challenge, particularly when involving open-shell radical intermediates. Here we present a cobalt-catalysed asymmetric radical hydroalkylation of 1,1-dialkyl-substituted alkenes with unactivated alkyl electrophiles, facilitating the formation of C(<i>sp</i><sup>3</sup>)–C(<i>sp</i><sup>3</sup>) bonds with simultaneous construction of traditionally unaccessible fully alkyl-substituted chiral tertiary carbon centres attaching substituents possessing similar steric and electronic properties. This enantioselective control does not rely on the assistance of heteroatoms or aryl functional groups as is often required in established approaches. Mechanistic studies indicate that the stereoselectivity primarily arises from the dispersion effect between catalyst and substrate, thereby avoiding substrate-specific constraints.</p><p></p>

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Catalytic asymmetric hydroalkylation of 1,1-dialkyl-substituted alkenes with unactivated alkyl electrophiles

  • 期刊论文

  • 发表日期：

    2026年1月13日

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  • Shucheng Ma,
  • Lihan Zhu,
  • Jianjun Yin,
  • Lianghua Wang,
  • Xiuping Yuan,
  • Simin Wang,
  • Dazhen Shi,
  • Qian Zhang,
  • Tao Xiong

摘要

Asymmetric addition to unsaturated double bonds provides an efficient strategy for the synthesis of optically active molecules. Despite advances over the past decades, achieving highly enantioselective transformations of purely alkyl-substituted 1,1-dialkylethenes has remained a challenge, particularly when involving open-shell radical intermediates. Here we present a cobalt-catalysed asymmetric radical hydroalkylation of 1,1-dialkyl-substituted alkenes with unactivated alkyl electrophiles, facilitating the formation of C(sp3)–C(sp3) bonds with simultaneous construction of traditionally unaccessible fully alkyl-substituted chiral tertiary carbon centres attaching substituents possessing similar steric and electronic properties. This enantioselective control does not rely on the assistance of heteroatoms or aryl functional groups as is often required in established approaches. Mechanistic studies indicate that the stereoselectivity primarily arises from the dispersion effect between catalyst and substrate, thereby avoiding substrate-specific constraints.