Studies On Preparation And Catalytic Performance Of Anew J(?)rgensen-hayashi Catalyst And Its Peg Supported Catalysts

Because of its unique structure,J(?)rgensen-Hayashi catalyst plays a decisive role in the field of asymmetric catalysis and synthesis,which not only can catalyze a series of asymmetric organic reactions with high efficiency and selectivity,but also greatly expand the application of the secondary amines.In this thesis,the recent advances of J(?)rgensen-Hayashi catalysts and the supported organic catalysts were summarized and reviewed.Based on the review of the literatures,the preparation and catalytic performance of a new J(?)rgensen-Hayashi catalyst and its PEG supported catalysts were studied.This dissertation includes the following three parts:(1)Some general examples of recent advances of the Jorgensen-Hayashi catalyst and the supported organic catalyst were summarized and reviewed.(2)A novel J(?)rgensen-Hayashi catalyst was synthesized through an effective synthetic route with high yield,and a new kind of recyclable and reusable PEG-supported Jorgensen-Hayashi catalyst was further synthesized through a thiol-ene coupling reaction for the first time.(3)Studies on the catalytic performance of the catalyst monomer and its PEG-supported catalysts:(a)the iminium ion catalyzed asymmetric Michael reaction of 4-Fluorocinnamaldehyde and dimethyl malonate catalyzed by the catalyst monomer has been accomplished,and the adducts were afforded in good yields(up to 99%)with good enantioselectivities(up to 93%ee);(b)the iminium ion catalyzed asymmetric Michael reaction of cinnamaldehyde and nitromethane catalyzed by the catalyst monomer has been accomplished,the adducts were afforded in good yields(up to 99%)with good enantioselectivities(up to 93%ee);(c)the enamine catalyzed asymmetric Michael reaction of a wide range of aldehydes with both nitroolefins and nitrodiene catalyzed by the catalyst monomer has been accomplished,the adducts were afforded in good yields(up to 99%)with good enantioselectivities(up to 99%ee)and diastereoselectivities(up to 99%dr);(d)Then the catalytic performance of the PEG-supported Jorgensen-Hayashi catalysts were studied.The catalyst was proven to be efficient for the enamine catalyzed asymmetric Michael reaction of a wide range of aldehydes with both nitroolefins and nitrodiene,the adducts were afforded in good yields(up to 95%)with good enantioselectivities(up to 99%ee)and diastereoselectivities(up to 99%dr).The prepared PEG-supported catalyst can be recovered eight times and it has similar diastereoselectivity and enantioselectivity with the unsupported functional monomer.