Pd(ii)-catalyzed -C-H bromination and chlorination of aniline and benzoic acid derivatives.

The classic electrophilic bromination leads to - and -bromination of anilines due to their electron-rich properties. Herein we report the development of an unprecedented Pd-catalyzed -C-H bromination of aniline derivatives using commercially available -bromophthalimide (NBP), which overcomes the competing /-selectivity of electrophilic bromination of anilines. The addition of acid additives is crucial for the success of this reaction. A broad range of substrates with various substitution patterns can be tolerated in this reaction. Moreover, benzoic acid derivatives bearing complex substitution patterns are also viable with this mild bromination reaction, and -C-H chlorination is also feasible under similar reaction conditions. The ease of the directing group removal and subsequent diverse transformations of the brominated products demonstrate the application potential of this method and promise new opportunities for drug discovery.