Preparation And Catalytic Properties Of Supported Chiral Diamine/ruthenium Catalysts

In this paper,we have synthesized two kinds of supported mesoporous catalysts,one is MesityleneRu BF₄ArDPEN@Me-FDU-12@BF₄-DABCO and the other is Pd@mesityleneRuArDPEN@PMO.In the first project,we developed a Me-FDU-12 carrier using triblock copolymers,trimethyltoluene,tetraethoxysilane and hexamethyldisilane.The bifunctional catalyst MesityleneRu BF₄ArDPEN@Me-FDU-12@BF₄-DABCO was formed by loading triethylenediamine and chiral diamine ruthenium catalyst onto the support of Me-FDU-12 by BF₄ anions,which ensured that the organic base catalyst and chiral diamine ruthenium catalyst were all in the pore channels of the support.The chiral?-amino alcohols were synthesized by one-pot Michael addition and asymmetric transfer hydrogenation reaction with aryl amines and unsaturated aryl ketones 1-phenylprop-2-en-1-one and their derivatives.The experimental results show that all the?-aminoalcohols obtained have a good yield?90%?and enantioselectivity?96%?.And the supported organic alkali catalyst played a good role in promoting the Michael addition in the first step.The catalytic activity of the catalyst did not change obviously,and the yield and ee value of the product?-aminoalcohol did not change significantly.In the second project,we used sodium salicylate and cetyltrimethylammonium bromideastemplates,Aflower-likemesoporouscatalyst,Pd@MesityleneRuDPENPEN@PMO,was successfully synthesized by using bis?3?triethoxy?propyl?-tetrasulfide and tetraethoxy silane and chiral Ts-DPEN silicon source,and supported with palladium nanoparticles by Tetrasulfide bond.The chiral diphenylethanolderivativesweresuccessfullysynthesizedbySuzuki coupling-asymmetric hydrogen transfer reduction of phenylboric acid derivatives and iodoacetophenone.The yield of chiral biaryl alcohol?99%?and ee value?98%?have obtained good results.We have carried out a cyclic application experiment on catalyst,which proves that catalyst can be reused seven times,but the efficiency of catalyst does not decrease.The catalyst has broad application prospect.