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Study On Catalytic Performance Of Supported Organometallic Catalysts For Imine And

Posted on:2015-05-25Degree:MasterType:Thesis
Country:ChinaCandidate:Z L WangFull Text:PDF
GTID:2271330431466953Subject:Organic Chemistry
Abstract/Summary:PDF Full Text Request
Chiral alcohols. amines are important intermediates in organic synthesis, in pesticide. medicine and fine chemical synthesis has been widely used, the asymmetric catalytic hydrogenation is one of methods to obtain chiral alcohol, amine compounds. Although a variety of highly active, high stereoselectivity of chiral ligands and catalyst were designed and synthesized, all kinds of new asymmetric catalytic methods and strategies were developed and successfully applied, all kinds of special and challenging aromatic ketone. imine important breakthrough in the substrate of hydrogenation. but aromatic ketone. imine asymmetric catalytic hydrogenation of imine still exist, such as low reactivity, the substrate scope narrow, harsh reaction conditions, catalyst is not easy to recycle and other issues. Therefore, development of more efficient, high selectivity, and environment friendly method of asymmetric catalytic is the future for the direction of the development of chiral alcohols. amines, compared to the hydrogenation. in recent years. the development of asymmetric catalytic transfer hydrogenation has many advantages, asymmetric transfer hydrogen refers to the presence of chiral catalysts, with other hydrogen donor except hydrogen source for hydrogen, reducing the reaction of chiral compounds. asymmetric transfer hydrogenation has emerged as an excellent method for the enantioselective reduction of unsaturated carbonyl and imine groups Because of the mild reaction conditions. simple operation and post-treatment process. hvdrogen donor tap cheaply(1) Synthesis of the corresponding benzaldehyde benzoin, in order to correspond annular imine synthesis, five or six-membered cyclic imide form a ring. on the lack of imine Z, E isomer problem, it is important to ring an organic imine intermediate body, mainly to the synthesis of chiral amines, chiral amines has been widely used in pesticide synthesis of pharmaceuticals and fine chemicals.(2) First, silica balls (50nm) graft on19%moL (S, S)-TsDPEN silicon source in the toluene solution.which made functionalized silica spheres, and then add [Cp*RhCl2]2in dichloromethane solution preparing SiO2-TsDPENCp*Rh catalyst. Second.(TEOS) and Ts-DPEN silicon source copolymerized in the water making functionalized mesoporous silica nanoparticle ball when cetyl-trimethylammonium tosylate (CTATos) acted as template.and then add [Cp*RhCl:|2in the methylene chloride solution to prerare heterogeneous MSN-TsDPENCp*Rh catalyst Third The above two kinds of catalysts in the ethyl acetate solution respectively with formic acid triethylamine (5:2) as the hydrogen source, respectively for4.5-diaryl cyclic sulfamidates asymmetrically transfer hydrogen reaction preparing double chiral amine or4-aryl amine preparing mono chiral. the MSN-TsDPENCp*Rh catalyst effect best conversion rate is more than99%. the ee value is97%. After it is used8times repeatedly, the catalytic activity and selectivity is not obviously reduced. SiO2-TsDPENCp*Rh the effect is the same asMSN-TsDPENCp*Rh catalyst. (3) Both polyhedral oligomeric silsequioxane (POSS) and triethoxy silane (HSi(OEt)3) are addition reaction to generates POSS silicon source, and then10%moL (S,S)-TsDPEN silicon source copolymerization to generate functional material of POSS and then added [Cp*IrCl2]2to produce heterogeneous catalyst, and then test it in water system of aromatic ketone asymmetric catalytic.
Keywords/Search Tags:asymmetric transfer hydrogenation, Functionalized silica catalyst, aromaticketone, 4,5-diaryl cyclic sulfamidates
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