The Application Of Chiral Ruthenium Catalysts In Asymmetric Hydrogen Transfer, Series Reaction And Their Catalytic Activity

Asymmetric hydrogen transfer(ATH)has been widely used in the production of pharmaceuticals,pesticides and fine chemicals,which is considered to be the most effective way to construct chiral alcohols and chiral amines.Asymmetric hydrogen transfer reaction,replacing hydrogen as hydrogen source,has many advantages,such as mild condition,low hydrogen source and so on.In the field of catalysis,adsorption,and biomedical sensors,organic functionalized mesoporous materials have attracted wide attention,since the hydrophobic mesoporous silicon material can improve the catalytic reaction rate,significantly improve the hydrothermal stability,and its efficiency on the adsorption of organic molecules,which have widely attention.In the part one,most of chiral benzyl alcohol are obtained by the hydrogenation of acetophenone,although the high yield and high stereoselectivity target compounds can be obtained,but the high pressure makes it difficult to operate.In addition to pure raw materials aryl sulfonyl methyl acetophenone also was got from benzyl acetophenone and aromatic sulfinic acid sodium nucleophilic substitution reaction,which makes the long production cycle,and high product cost.In this chapter,para bromoacetophenone and benzyl methyl benzene sulfinic acid sodium as substrate,the reaction conditions of the synthesis of intermediate products were aromatic sulfonyl methyl acetophenone,and a string of united into the best catalyst of chiral aryl sulfonyl methyl benzene ethanol;then through one pot catalytic multi-step organic reaction with sodium formate as hydrogen the source,using benzyl acetophenone and sodium benzoate as substrate,and then through a series of asymmetric hydrogen transfer got the synthesis of chiral products.The external conflict problem of the one pot reaction can be overcome,and the sulfonyl group can also be left without racemization.In the part two,we based on N,N,N-1-sixteen alkyl three methyl bromide as hard template,four ethyl silicate as the main skeleton of silicon source,(S,S)-4-(trimethoxy silyl)benzene sulfonyl-1,2-two phenyl two amine as chiral functional silicon source,and used two chloro two phenyl silicone hydrophobic function source as silicon source,then we preparated hydrophobic mesoporous catalyst precursor;at last coordinated with five methyl cyclopentadienyl ligand rhodium chloride,we got the hydrophobic functional rhodium catalyst.Through a series of characterizations of catalysts,we got the target catalyst successfully;and applicated it to asymmetric catalysis of 3-(argiomethyl)isobenzofuran-1(3H)-one,which showed good catalytic activity and enantioselectivity of the catalyst;and it is easy to recovery and has stable structure.It can reuse 8 times and no activity significantly decreased.