The Application Of Hydrophilic Materials In Heterogeneous Asymmetric Reduction Of ?-trifluoromethylimine And The One-pot Synthesis Of ?-hydroxy Sulfone

Chiral alcohols and chiral amines are common organic compounds,which widely exists in nature.They have important applications in pesticides,pharmaceuticals,fine chemicals and other fields.How to efficiently get chiral alcohols and amines are hot research in recent decades.Many catalysts and methods have been developed.Asymmetry reduction of the corresponding prochiral ketones,imines(metal-hydrogen reduction,hydrogenation,transfer hydrogenation)is an effective way to obtain these types of chiral compounds.Compared to hydrogenation,other cheaper hydrogen donor be used instead of hydrogen.So reaction condition of asymmetric hydrogen transfer is mild and the operation is simple.And it is rapidly developing these years.Heterogenous catalysts have not only solved problems of recycling but also overcomed the issues of environmental polution.The great perspective of this kind of catalyst caught many scientists' eyes.And in the area of multiphase reaction,mesoporous silica materials have always been playing crucial roles.(1): Organoruthenium-functionalized mesoporous silica nanospheres are prepared through the co-assembly of chiral 4-(trimethoxysilyl)ethyl)phenylsulfonyl-1,2-diphenylethylene-diamine and tetraethoxysilane followed by complexation with an organoruthenium complex.(RuTs-DPEN-PEG-PEOS)was prepared as a carrier to obtain a heterogeneous phase catalyst which exhibited a homogeneous catalyst equivalent to that of a homogeneous catalyst,and a hydrophilic organic-inorganic hybrid silicon material was synthesized as a carrier.Of the catalytic activity and enantioselectivity.The asymmetric hydrogen transfer reaction of the catalyst in the aqueous phase was systematically studied.It was equivalent to the homogeneous catalyst in catalytic activity and stereoselectivity.More importantly,the heterogeneous catalyst was Imine compounds for asymmetric hydrogen transfer can be easily recovered by centrifugation and recycling,recycling 8 times still maintain a good catalytic activity and stereoselectivity.Showing its broad prospects and potential application value in catalytic synthesis.(2): Chiral ?-hydroxysulfones are one of the most important optically active alcohols,and are also essential for several bioactive molecules.Because of the strong electron-withdrawing properties of the sulfonyl groups at the ?-position,the carbon at the ?-position can be further functionalized,and the sulfonyl groups can leave without racemization.Chiral ?-hydroxysulfones are also often used Synthesis of optically active compounds.Most of the chiral ?-hydroxysulfone compounds are currently obtained by pressurized hydrogenation of the ?-ketone sulfone compound,although high yield and high stereoselectivity of the target compound can be obtained,but the high pressure reaction makes them difficult to operate.In addition,the raw material ?-ketone sulfone compounds are also required to be produced by nucleophilic substitution reaction of ?-bromindanone substitutes and sodium p-phenylene sulfinate,which requires a long production and high cost product.Therefore,we designed the synthesis of chiral ?-hydroxy sulfone target compounds directly from ?-bromoindone substitutes and sodium p-phenylene sulfonate as a raw material to obtain high ee and dr.