Demonstrates effective coupling of α-bromoamides and alkylzirconocenes, suggesting a new method for amide synthesis.
) coupling of racemic α-bromoamides with alkylzirconocenes generated in situ from unactivated alkenes is reported. This transformation exploits alkene-derived alkylzirconocenes as redox-active alkyl partners, enabling direct access to enantioenriched α-tertiary aliphatic amides without an external photocatalyst or reductant. Photoinduced C-Zr bond homolysis generates alkyl radicals for capture by a chiral nickel catalyst, while the resulting zirconocene species is proposed to facilitate reductive nickel turnover. The reaction accommodates a range of alkenes and α-bromoamides, delivering the desired products in moderate to good yields and up to 94% ee. The practicality of this method is demonstrated by a scale-up reaction and downstream derivatization of the amide products.
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Chen et al. (2026) studied this question.
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