Switching the hydrogenation selectivity of urea derivatives via subtly tuning the amount and type of additive in the catalyst system.

Catalytic hydrogenation of urea derivatives is considered to be one of the most feasible methods for indirect reduction functionalization of CO 2 and synthesis of valuable chemicals and fuels. Among value-added products, methylamines, formamides and methanol are highly attractive as important industrial raw materials. Herein, we report the highly selective catalytic hydrogenation of urea derivatives to N -monomethylamines for the first time. More importantly, two- and six-electron reduction products can be switched on/off by subtly tuning 0.5 mol% KO t Bu (2% to 1.5%): when the molar ratio of KO t Bu/(PPh 3 ) 3 RuCl 2 exceeds 2.0, it is favorable for the formation of two-electron reduction products ( N -formamides), while when it is below 2.0, the two-electron reduction products are further hydrogenated to six-electron reduction products ( N -monomethylamines and methanol). Furthermore, changing the type of additive can also regulate this interesting selectivity. Control experiments showed that this selectivity is achieved by regulating the acid-base environment of the reaction to control the fate of the common hemiaminal intermediate. A feasible mechanism is proposed based on mechanistic experiments and characterization. This method has the advantages of being simple, universal and highly efficient, and opens up a new synthesis strategy for the utilization of renewable carbon sources.