Visible-Light-Induced Nickel-Catalyzed Enantioconvergent C(sp <sup>3</sup> )–C(sp <sup>3</sup> ) Coupling of α-Bromoamides with Alkene-Derived Alkylzirconocenes

) 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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Publication Details

Journal
Organic Letters
Published
2026-07-01
DOI
https://doi.org/10.1021/acs.orglett.6c02296
Primary Topic
Radical Photochemical Reactions
Type
article
Field-Weighted Citation Impact
0.00

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article

Visible-Light-Induced Nickel-Catalyzed Enantioconvergent C(sp 3 )–C(sp 3 ) Coupling of α-Bromoamides with Alkene-Derived Alkylzirconocenes

Huifeng Yue, Lujie Chen, Jianguo Han
Organic Letters
Radical Photochemical Reactions
article

Visible-Light-Induced Nickel-Catalyzed Enantioconvergent C(sp 3 )–C(sp 3 ) Coupling of α-Bromoamides with Alkene-Derived Alkylzirconocenes

Huifeng Yue, Lujie Chen, Jianguo Han
article en

Abstract

) 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.

Organic Letters
Chemical Synthesis Lab (SG), Fuzhou University (CN)
National Natural Science Foundation of China
Openalex Percentile: Top 14%
Radical Photochemical Reactions
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