Catalytic Desaturation and fl-Fluorination of Aliphatic Amides Enabled by an Oxidative-Promoted Bond Destabilization

Described herein is the development of a desaturation and beta-fluorination reaction of cyclic amides, which is achieved by an oxidative-promoted selective hydrogen atom-transfer/isomerization/electrophilic fluorination process. Moreover, the combination of an N-hydroxy catalyst and Selectfluor allows alpha, beta-dehydrogenation and gamma-di-fluorination of N-aryl lactams to be established. Furthermore, the present selective catalysis also works well for the C-N bond cleavage of acyclic amides at the less crowded site. The mechanism of this reaction has been carefully illustrated with experimental and computational studies.

Automated summary

This study describes the development of a desaturation and beta-fluorination reaction of cyclic amides, which is achieved through an oxidative-promoted selective hydrogen atom-transfer/isomerization/electrophilic fluorination process. Furthermore, the discovery also allows for alpha, beta-dehydrogenation and gamma-di-fluorination of N-aryl lactams.