Base-Catalyzed Lossen Rearrangement: Modular Synthesis of α-Fluoroamides

Herein, we have developed a cascade reaction, which constructs C-N, C-C, and C-F bonds in a one-pot process through a base-catalyzed Lossen rearrangement of dioxazolones. The key to the success of this process lies in utilizing the base-catalyzed Lossen rearrangement of dioxazolones and the zwitterionic nature of the phosphorus ylides. This cascade reaction protocol integrates C-F bond formation and amide bond formation into a single process, enabling the efficient preparation of a wide range of structurally diverse α-fluoroamides. These compounds are otherwise difficult to obtain through such a modular approach using alternative methods.