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1,4-Aryl migration in ketene-derived enolates by a polar-radical-crossover cascade

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  • Niklas Radhoff

    (Westfälische Wilhelms-Universität)

  • Armido Studer

    (Westfälische Wilhelms-Universität)

Abstract

The arylation of carboxylic acid derivatives via Smiles rearrangement has gained great interest in recent years. Both radical and ionic approaches, as well as radical-polar crossover concepts, have been developed. In contrast, a reversed polar-radical crossover approach remains underexplored. Here we report a simple, efficient and scalable method for the preparation of sterically hindered and valuable α-quaternary amides via a polar-radical crossover-enolate oxidation-aryl migration pathway. A variety of easily accessible N-alkyl and N-arylsulfonamides are reacted with disubstituted ketenes to give the corresponding amide enolates, which undergo upon single electron transfer oxidation, a 1,4-aryl migration, desulfonylation, hydrogen atom transfer cascade to provide α-quaternary amides in good to excellent yields. Various mono- and di-substituted heteroatom-containing and polycyclic arenes engage in the aryl migration reaction. Functional group tolerance is excellent and substrates as well as reagents are readily available rendering the method broadly applicable.

Suggested Citation

  • Niklas Radhoff & Armido Studer, 2022. "1,4-Aryl migration in ketene-derived enolates by a polar-radical-crossover cascade," Nature Communications, Nature, vol. 13(1), pages 1-10, December.
    • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-30817-3
    DOI: 10.1038/s41467-022-30817-3
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