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

Niklas Radhoff and Armido Studer ()
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Niklas Radhoff: Westfälische Wilhelms-Universität
Armido Studer: Westfälische Wilhelms-Universität

Nature Communications, 2022, vol. 13, issue 1, 1-10

Abstract: 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.

Date: 2022
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DOI: 10.1038/s41467-022-30817-3

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