Manganese-catalyzed Borrowing Hydrogen Reaction And Quinones Synthesis

Metal catalysts are often needed in the field of organic synthesis,and the transition metal manganese has a very important application value in the field of catalysis because of its special catalytic performance and low price.Borrow hydrogen reaction is a green and efficient synthetic method in the organic synthesis and medicinal chemistry,and that quinone derivatives also have many potential pharmaceutical application value.So the study of their synthesis has im portant significance.This article synthesizes some different types of manganese catalyst and these catalysts are used in the hydrogen reaction and the synthesis of quinone derivatives.The main contents are as follows:1.The application of manganese and three azole ligands in the synthesis of quinone derivativesA series of ferrocene triazole ligands were designed and synthesized.The structures of the compounds were confirmed by NMR and mass spectrum.The manganese/ferrocene triazole coordination system was applied to the reaction system of phenylhydrazine and phenylboronic acid.After optimizing the conditions,the optimal experimental conditions were obtained.The reaction yield of phenylhydrazine and phenylboronic acid was 94%.Under the optimal conditions,the universality of the substrate was studied with moderate to good yields.Extending the application of manganese/alanine triazole catalyst system in the reaction of p-QMs and dibenzoylmethane,it can also generate C-C bonds with good yield.A new method for the synthesis of quinone derivatives has been developed.2.Synthesis of TiO₂@MnO₂ composite catalyst and its application in the borrowing hydrogen reactionThe nano TiO₂@MnO₂ composite catalyst was prepared.Its appearance,structure and element composition were analyzed by SEM,TEM,EDS,XPS,XRD.We can get the best yield of 84%with TiO₂@MnO₂ as a catalyst,NaOH as a base,and toluene as a solvent at room temperature.Subsequent substrate expansion experiments have good reaction yields.The experimental results show that the composite catalyst has good catalytic performance.The catalytic system expands the reaction types of acetophenone with benzyl alcohol and a new method for the synthesis of 1,5-dione has been developed.3.Synthesis of Ag@MnO₂ catalyst and its application in the synthesis of benzoate and quinone derivativesThe nano Ag@MnO₂ composite catalyst was prepared.The morphology,element and structure of the composite catalyst were analyzed by XRD?SEM?TEM?XPSand EDS.Finally,the catalyst was applied to the reaction of phenylacetonitrile with tert-butyl hydroperoxide,tert-amyl hydroperoxide and cumyl hydroperoxide to form C-O bonds to generate benzoic acid ester compounds.After optimizing the experimental conditions,the optimal experimental conditions were selected and substrate development was carried out,with good to excellent yields,indicating that the composite catalyst has good catalytic performance.At the same time,it is applied in the reaction of p-QMs with diphenylphosphine and phosphorous ester to obtain a good yield..The composite catalyst also has excellent catalytic performance for this reaction.