A General Palladium-Catalyzed Amination of Aryl Halides with Ammonia

A study was conducted to demonstrate palladium(Pd)-catalyzed amination of aryl halides with ammonia. The active catalyst was formed in situ from Pd(OAc)2, along with air- and moisture stable phosphines as pre-catalysts. It was found that the productivity of the catalyst system was similar to that of competitive Pd and phosphine systems. It was demonstrated that the novel electron-rich sterically demanding phosphine ligand was unable to be displaced from the palladium by ammonia to a significant extent, which prevented the deactivation of the catalyst by the ligand. It was also demonstrated that the Pd-catalyzed animation worked at ambient pressure. It was observed that the optimized system showed an excellent substrate scope including deactivated, electron-neutral, and activated halides, o-, m- p-substituted substrates, aryl chlorides, and heterocycles.