Oxygen Migration–Defluorination Strategy Enables the Aminocarbonylation of Enaminones with o-Aminobenzamides and CF2Br2

The development of different concept approaches and user-friendly carbonyl surrogates for aminocarbonylation is highly desirable. Herein, we report the photocatalytic aminocarbonylation of enaminones with easily available o-aminobenzamides and CF2Br2 through an oxygen migration-defluorination strategy. The reaction features switchable transformation for the construction of carbamoyl-substituted enaminones and enol products and allows the expedient synthesis of fully substituted maleimides under mild reaction conditions.