Synthesis Of A Class Of Zirconium Phosphonate Suspend With(1R,2R)-1,2-diphenylethane Diamine Supported Ru Catalyst And Their Application In Asymmetric Transfer Hydrogenation Reaction

In this paper, a series of phosphonates with the different arm lengths (n=2,4and6) had been synthesized through selective sulfonadation, radical addition and hydrolysis reactions by using (1R,2R)-1,2-diphenylethane diamine as raw material. The phosphonates5a-c could react with ZrOCl2in various solvents to obtain zirconium phosphonates6a-H, M, A, I, F, O and6b, c-F with different surface morphologies. Then the supported Ru catalysts6a-H, M, A, I, F, O-Ru and6b, c-F-Ru were prepared by the complexation reaction of amino with [RuCl2(p-cymene)]2.The composition, structure and morphology of (1R,2R)-1,2-diphenylethane diamine-appended zirconium phosphonates and their supported Ru catalysts were characterized by IR, DTG, N2adsorption and desorption isotherms, SEM, HRTEM and XPS.Using the asymmetric transfer hydrogenation of1-(3-methoxyphenyl)-2-phenyl-ethane-1,2-dione as model reaction, the effects of zirconium phosphonate-supported Ru catalyst, used amount of catalyst, solvent, S/C, the mole ratio of HCO2H/NEt3and temperature on catalytic performance had been screened in details. Under the optimum reaction conditions:6a-F-Ru, S/C=120, VHCOOH/VEt3N=1:2,0.3mL CH3CN,50℃,40h, the catalytic performances of6a-F-Ru in asymmetric transfer hydrogenation of1,2-diphenyldione and their derivatives had been investigated. The best results were88.5%yield,99.2%e.e., d.r.=29.4:1. After the completion of reaction,6a-F-Ru could be recycled by adding ethyl acetate.