Asymmetric Michael Addition And Bicatalytic Cyclization Of Nitrodiene Alkynes

Michael addition reaction is one of the most important methods which construct C-C bond.This paper mainly expounds that chiral nickel(Ⅱ)-diamine catalyst catalyze Michael addition reaction between conjugated nitro diengnes with diethyl malonate.And cyclohexanone was synthesized by the double acid catalytic cyclization reaction.Michael addition reaction is one of the most important methods of construct C-C bond.This paper mainly expounds that chiral nickel(Ⅱ)-diamine catalyst catalyze Michael addition reaction between conjugated nitro diengnes with diethyl malonate.The addition products are 1,3-enynes.The first part of this paper describes Michael addition reaction and history on the nitroolefin of Michael addition reaction and research progress of conjugate nitro dienynes of Michael addition reaction.The second part is the design of the subject,the experimental research method and the experiment results and discussion.The third part is the part of the experimental steps and data.This paper elucidates Michael addition reaction between conjugated nitro diengnes with diethyl malonate using chiral nickel(Ⅱ)-diamine as catalyst.The results indicated that chiral nickel(Ⅱ)-diamine would give excellent yield(99%)and super enantioselectivity(91%),when the reaction occurred in meta-xylene and 10 mol%catalyst and suffering of 54 h at room temperature.Then,we developed a new method that turn 1,3-enynes to cyclohexanone through double acid catalytic cyclization reaction.We observed that the cyclization is catalyzed by both the p-toluene sulfonic acid and the three fluorine mesylate indium.The results indicated that the optimum condition was solvent for DCE:H2O=1:4(equivalent),reflux 9 hours under 83℃.In addition,the substrates are extensive for the different substituents which have an effect on reaction time.To sum up,we found a novelty way to get the Michael addition reaction between conjugated nitro diengnes with diethyl malonate using chiral nickel(Ⅱ)-diamine as catalyst.And we use a novelty method to get the cyclohexanone compounds,which are intermediates of drugs and natural products.