Synthesis Of Polymer-modified Supported Catalysts And Their Applications In Substitution/reduction Reactions

In recent years,the research on inorganic silicon-based mesoporous ball-loaded chiral organometallic catalysts has achieved great success,and has attracted wide attention from scientists because of its simple preparation process,easy modification and environmental friendliness.However,due to the diffusion problem of the inorganic silicon-based mesoporous-supported chiral organometallic catalyst in the reaction system,the catalytic reaction rate is slow.In this paper,this paper is aimed at this shortcoming.The polymer modification strategy is adopted to improve the reaction rate of the catalytic reaction by modifying the polymer of the inorganic silicon-based mesoporous beads,thereby improving the catalytic efficiency of the catalyst.The research content of this thesis is reflected in the following two aspects.(1)Preparation of a lipophilic polycaprolactone-modified supported chiral quinone/diamine catalyst and its application in the synthesis of chiral ?-hydroxy sulfone in a one-pot method;this paper uses cetyltrimethyl The ammonium chloride is used as a template,and the functionalized silicon-based mesoporous beads obtained by copolycondensation of ethyl orthosilicate and chiral diamine are grafted with a lipophilic polymer,followed by coordination with an organic hydrazine to obtain a polymer modification.Chiral oxime/diamine catalyst;optimized reaction conditions for aromatic ketones and sulfonyl salts under ethyl acetate conditions were obtained by optimization of catalytic reaction conditions;substitution/no was achieved by extension of series substrates The catalytic efficiency is improved in the one-pot reaction of symmetric hydrogen transfer reduction;the effective preparation of a series of chiral ?-hydroxy sulfones is completed,and the yield is as high as 99% and the selectivity is high(the enantioselective ee value is up to 99%).The diastereoselective selectivity can reach 99:1);the catalyst can be reused seven times and still maintain high catalytic performance.(2)Preparation of Hydrophilic Polyethylene Glycol Modified Supported Chiral Cerium/Diamine Catalysts and Preparation of Chiral Mesoporous Chiral Supported Metal Catalysts in One-Pot Method and Their Synthesis of Chiral ?-Hydroxysulfones Application in this paper;using cetyltrimethylammonium chloride as template as a template,silicon-based mesoporous beads obtained by co-condensation of tetraethyl orthosilicate as a skeleton and a chiral diamine,and then grafting a hydrophilic polymer Then,coordination with the organic hydrazine to obtain a polymer-modified chiral quinone/diamine catalyst;by optimizing the catalytic reaction conditions,an aromatic ketone under the conditions of isopropanol:water(3:1,v:v)is obtained.Optimized reaction conditions with sulfonyl salts;improved catalytic efficiency in a one-pot reaction of substitution/asymmetric hydrogen transfer reduction by extension of a series of substrates;complete preparation of a series of chiral ?-hydroxy sulfones,It has achieved 99% yield and high selectivity(enantiomer selectivity ee value up to 99%,diastereoselective de value up to 99:1);catalyst can be reused eight times to maintain high catalytic performance.