The Effect Use Of Heterogeneous Rhodium Catalyst In Asymmetric Hydroamination

Heterocyclic with Nitrogen is a series of useful compounds that are widely applied in pharmaceuticals and fine synthetic fields which draws many attentions from the synthetic scientists. Hydroamination is the reaction of one-step synthesizing heterocyclic by C=C or C=C bond with N-H bond, which has great advantage in economical field. However, there is no heterogeneous catalyst that has been reported as far as we know. Here, we report an asymmetric hydroamination catalysis of the heterogeneous catalyst with immobilized rhodium as activity center and inherent sulfhydryl of mesoporous silica (SBA-15materials) as host. The main results in our work are listed as follows:1. The rhodium catalyst selected for immobilization in this work is MOP-Rh, an efficient homogeneous catalyst for hydroamination. To further enhance the catalytic efficiency, another heterogeneous catalyst was designed. The results of PXRD, nitrogen adsorption/desorption isotherms of the supports images show that the support SBA-15’s well-defined hexagonally symmetric channel structure. TEM demonstrates that the heterogeneous catalyst also has the well-defined hexagonally symmetric channel structure.13C NMR and31P NMR verify the success of immobilization.2. The asymmetric hydroamination of Benzyl (2,2-diphenyl-4-pentenyl) amine is used to research the heterogeneous Rh catalyst. In48h and60℃, the, heterogeneous catalyst which contained40%2-(Dicyclohexylphosphino)binaphthyl reveales the best yield, up to2.77%, and the best e.e., up to33%.3. The heterogeneous catalysts were also used to catalyze the asymmetric addition of olefin and aldehyde. Until now, the results have not achieved the expection.