Computational Analysis on the Pd-Catalyzed C–N Coupling of Ammonia with Aryl Bromides Using a Chelate Phosphine Ligand

The Buchwald–Hartwig amination of arylhalides with the Pd–Josiphos complex is a very useful process for generation primary amines using ammonia as reactant. Density-functional theory (DFT) calculations are carried out to examine reaction mechanism this process. Although general C–N cross-coupling known, there still some open questions regarding effect chelate phosphine ligand and role base in Reaction pathways involving release one arms compared those where remains fully coordinated. Conformational analysis required properly evaluate proposed pathways. played by added (t-BuO–) possible or just was also evaluated. understanding all these aspects allowed us propose complete Pd-catalyzed coupling Josiphos ligand.