Rh(I)-Catalyzed Coupling of Azides with Boronic Acids Under Neutral Conditions

Because of the importance of polyfunctional amines, C-N bond formation is important in synthetic organic chemistry. Here we present a neutral amination reaction using azides as the nitrogen source and arylboronic acids with a rhodium(I) catalyst to afford alkyl-aryl and aryl-aryl secondary amines. Natural products and pharmaceutical derivatives were applied, and gram-scale reactions were performed, which demonstrated the utility. Mechanistic experiments and DFT calculations suggested that the reaction involves a metal-nitrene intermediate.

Automated summary

Due to the importance of polyfunctional amines, the formation of C-N bonds is crucial in synthetic organic chemistry. This study presents a neutral amination reaction utilizing azides as the nitrogen source and arylboronic acids with a rhodium(I) catalyst, leading to the synthesis of alkyl-aryl and aryl-aryl secondary amines. The utility of this method was demonstrated through the application to natural products and pharmaceutical derivatives, as well as gram-scale reactions. Mechanistic experiments and DFT calculations indicated the involvement of a metal-nitrene intermediate in the reaction.