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

Automated summary

The Buchwald-Hartwig amination of arylhalides with the Pd-Josiphos complex using ammonia as a reactant is a useful process for primary amine synthesis. Density-functional theory calculations were used to examine the reaction mechanism, revealing the importance of the chelate phosphine ligand and base in the process. The study allowed for the proposal of a complete reaction mechanism for the Pd-catalyzed C-N coupling reaction.