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

Described herein is the development of a desaturation
and β-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 α, β-dehydrogenation and
γ-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.

本发明涉及环状酰胺的去饱和及β-氟化反应的研究，该反应通过氧化促进的选择性氢原子转移/异构化/亲电氟化过程实现。此外，N-羟基催化剂与Selectfluor的结合，可确立N-芳基内酰胺的α,β-脱氢及γ-二氟化。进一步地，本选择性催化方法亦适用于非环状酰胺在较不拥挤位置的C-N键断裂。本反应的机理已通过实验和计算研究得到了细致的阐释。