Amino Acid-Derived Schiff Base Metal Complexes Catalyzed Asymmetric Reactions Of Unsaturated Carbonyl Compounds

With the research on natural products and the continuous development of modern medicine,the research of chiral compounds has attracted more and more attention from organic chemists.Organic chemists mainly fucos on on two-aspect chiral compounds,one is to study new catalysts,and the other is to study new asymmetric reactions.We studied the asymmetric reaction catalyzed by metal salt based on the asymmetric catalytic system of our laboratory.This dissetation is mainly composed of the following three parts.In the first part,chemoselective and enantioselective Friedel-Crafts 1,2-addition of ?,?-unsaturated ?-ketoesters with pyrrole catalyzed by copper complexBased on asymmetric Friedel-Crafts 1,4-addition of pyrrole and ?,?-unsaturated?-ketoesters researched by our laboratory,the asymmetric Friedel-Crafts 1,2-addition of pyrrole was achieved.In the optimization of a series of ligands,we found that a chiral phenylalanine-derived Schiff base ligand and copper coordination catalyst could effectively catalyze the reaction to afford the corresponding products with good yields and good enantioselectivities.In the second part,enantioselective Michael reaction of ?,?-unsaturated acylpyridiniums oxynitrides with nitroacetate catalyzed by copper complexWe choose nitroacetate as a stable carbanion donor,?,?-unsaturated acylpyridiniums oxynitride as a stable Michael acceptor.The asymmetric Michael reaction of nitroacetate to ?,?-unsaturated acylpyridinium oxynitride was achieved.Under the catalyst of the coordination of a proline-derived tridentate ligand and copper complex,the corresponding products could be obtained with high yields and high enantioselectivities.In the third part,enantioselective Friedel-Crafts reaction of ?,?-unsaturated acylpyridiniums oxynitride with pyrrole catalyzed by zinc complex in water.Based on the chiral Schiff base-derived aqueous ligands developed in our laboratory,asymmetric Friedel-Crafts reaction of pyrrole with ?,?-unsaturated acylpyridiniums oxynitride was achieved in the aqueous phase.After a series of optimizations,we achieved this asymmetric Friedel-Crafts reaction in aqueous media under mild conditions.