Cobaloxime Photocatalysis for the Synthesis of Phosphorylated Heteroaromatics.

Herein, cobaloxime is used for the first time as a catalyst for the synthesis of phosphorylated heteroaromatics, which is an intriguing and versatile functional motif. With visible‐light irradiation, cobaloxime not only oxidizes phosphine oxides to form phosphorus radicals (P‐radicals) for a subsequent reaction with radical acceptor isocyanides or heteroaromatics, but also combines the radical intermediate with β‐H elimination, thereby producing phosphorylated heteroaromatics with only H2 or CH4 as byproduct. Phosphine oxides with dialkyl, alkylaryl, and diaryl substituents could be directly transformed into phosphorylated phenanthridines, benzothiazoles, isoquinolines, and common heteroaromatics. This catalytic system features extremely mild conditions, broad substrate scope and good to excellent yields. Scale‐up reaction and sunlight reaction show the great application potential in the green synthesis of important organophosphorus chemicals. [ABSTRACT FROM AUTHOR]