Heterogeneous Ru/TiO 2 for hydroaminomethylation of olefins: multicomponent synthesis of amines

Synthesizing amines via the hydroaminomethylation (HAM) reaction of olefins, a multicomponent reaction, has been regarded as one of the most attractive methods compared with the traditional methods considering the atom economy and environmental friendliness. However, the use of homogeneous catalysts, complex ligands containing diphosphine or nitrogen, and base or acid additives has severely hampered the utilization of these methods. Herein, an efficient heterogeneous Ru/TiO 2 -catalyzed HAM reaction of olefins is developed without any additives. Various amines, including secondary and tertiary amines, can be successfully obtained from olefins including aromatic and aliphatic olefins. Systematic studies demonstrate the lower electron density of Ru δ+ and the higher number of acid sites of Ru/TiO 2 , leading to the high HAM reaction activity of olefins. Most importantly, nitrobenzene derivatives can also be transformed to the corresponding products over Ru/TiO 2 in excellent yields.