The Michael Reaction Confining 3-Phenacylideneoxindoles And A New Catalyst For Catalytic Oxidation Of Indole Henry Reaction

The development of asymmetric organiccatalytic reaction is only several decades,the development of applying cinchona alkaloid and its derivatives in asymmetric reactions is about a decade years,but the cinchona alkaloid and its derivatives as a catalyst can catalyze multiple reactions which has obvious achievements in the laboratory and the application of drug.However,there are problems that need to be addressed in the following several aspects:(1)Using known cinchona alkaloid catalysts and their derivatives,extending new reaction type.(2)Using known catalytic activity groups,building a new,wider application range,better catalytic effect multifunctional cinchona alkaloid derivatives catalyst.This thesis is based on the current research status and has done two parts.The first part,3-phenacylideneoxidole of 1a-j can react with nitromethane under alkaline catalyst belong to the new synthetic method of Michael reaction,used chiral quinine thiourea classes of organic small molecules as chiral catalyst,The hydrogen bond activation mechanism is used to control the stereostructure of the product.Filtered catalytic conditions at room temperature,toluene as solvent,the absence of additives,with a high yield of 97-99 %,a new type of chiral asymmetricm-lactamide with nitro,carbonyl and other reactive groups was obtained.The synthesis of 10 types of chiral gamma-lactamide has a good enantioselectivity(ee value 62% to 99%ee)The second part,on the basis of the structure of cinchonine,it was improved through the Mitsunobu reaction,the two new kinds of ethers were prepared by combining quinine or quinine with the structure of the bionaphthol with axial chirality.With chiral 1 naphthol instead of quinoline structure of quinine,alcohol as chiral quinine loop instead of quinine in kratos nuclear structure,through the Mitsunobu reaction ether bond formation.Two kinds of new simulation cinchona alkaloid structure by catalyst introduced hydroxyl and synchronization in the center of chiral axis into a chiral structure.In the asymmetric Henry reaction of 2,3-oxindole and nitromethane,the high yield(99%)of the product were obtained by the addition of ee 10% under the new 2 catalysts.