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<p>Transition-metal-catalysed enantioselective transformations with allylic electrophiles are widely used for synthesizing chiral small molecules, including natural product and pharmaceuticals. Current approaches for the allylic addition to carbonyls focus on γ-selective allylation, with linear-selective approaches remaining challenging owing to the inversion of the six-membered Zimmerman−Traxler type transition state. Here we present a cobalt-catalysed enantioselective reductive α-selective allyl addition to ketimines using stereoselective radical addition, which allows access to homoallylic amino esters with excellent enantioselectivity and functional group tolerance. This protocol is also applicable to three-component transformations of α-imino esters to generate α-tetrasubstituted amino acid derivatives, and its utility was demonstrated in a cascade in combination with a C–N coupling reaction to deliver pipecolinic acid derivatives. Mechanistic studies and computational calculations indicate that the enantio- and linear-regioselectivity of these reactions stems from the stereoselective addition of the allyl radical species to the cobalt-chelated imine intermediate.</p><p></p>

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Enantio- and linear-selective allylic radical addition to imines using reductive cobalt catalysis

  • 期刊论文

  • 发表日期：

    2026年1月19日

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  • Xianqing Wu,
  • Yue Shi,
  • Chenhuan Zhang,
  • Kejie Xu,
  • Tingting Xia,
  • Genping Huang,
  • Jingping Qu,
  • Yifeng Chen

摘要

Transition-metal-catalysed enantioselective transformations with allylic electrophiles are widely used for synthesizing chiral small molecules, including natural product and pharmaceuticals. Current approaches for the allylic addition to carbonyls focus on γ-selective allylation, with linear-selective approaches remaining challenging owing to the inversion of the six-membered Zimmerman−Traxler type transition state. Here we present a cobalt-catalysed enantioselective reductive α-selective allyl addition to ketimines using stereoselective radical addition, which allows access to homoallylic amino esters with excellent enantioselectivity and functional group tolerance. This protocol is also applicable to three-component transformations of α-imino esters to generate α-tetrasubstituted amino acid derivatives, and its utility was demonstrated in a cascade in combination with a C–N coupling reaction to deliver pipecolinic acid derivatives. Mechanistic studies and computational calculations indicate that the enantio- and linear-regioselectivity of these reactions stems from the stereoselective addition of the allyl radical species to the cobalt-chelated imine intermediate.