Manganese-Catalyzed Dehydrogenative Synthesis of Urea Derivatives and Polyureas

Urea derivatives have significant applications in the synthesis of resin precursors, dyes, agrochemicals, and pharmaceutical drugs. Furthermore, polyureas are useful plastics with applications in coating, adhesive, and biomedical industries. However, the conventional methods for the synthesis of urea derivatives and polyureas involve toxic reagents such as (di)isocyanates, phosgene, CO, and azides. We present here the synthesis of (poly)ureas using much less toxic reagents-(di)amines and methanol-via a catalytic dehydrogenative coupling process. The reaction is catalyzed by a pincer complex of an earthabundant metal, manganese, and liberates H2 gas, valuable by itself, as the only byproduct, making the overall process highly atomeconomic. A broad variety of symmetrical and unsymmetrical urea derivatives and polyureas have been synthesized in moderate to quantitative yields using this catalytic protocol. Mechanistic insights have also been provided using experiments and DFT computation, suggesting that the reaction proceeds via an isocyanate intermediate.