Theoretical Study On The Mechanism Of Copper-Catalyzed Synthesis Of Imidazolones And Indoline-2, 3-diones Reaction

In recent years, transition metal catalyzed cross-couplingreaction is developing very rapidly, and they play an extremelyimportant role in synthesis organic chemistry. Transition metalcatalyzed cross-coupling reactions under mild condition whichprovide the necessary conditions for our research. Common transitionmetal catalysts of palladium and copper, palladium due to itsexpensive price and a greater impact on the environment, thus limitedits application in some coupling reactions. Recently, copper as aninexpensive and less toxic transition metal catalyst in syntheticorganic chemistry plays an irreplaceable role.In this study, the mechanisms of copper-catalyzed synthesis ofimidazolones and indoline-2, 3-diones were studied using theaccurate quantum chemical calculation method. Our research isconducted on the basis of experiment, through design these tworeactions reasonable reaction process, then put forward theircomprehensive reaction mechanism, and in the actual process oftheoretical research, we found and make sure that these tworeactions in the experimental conditions of the respective optimalreaction channel, these results of this study not only for the synthesisof new substances to provide a solid and strong theoreticalfoundation, but also has important guiding significance. The main content of this work show that:1. Theoretical study on the mechanism of copper-catalyzed C-Ncoupling synthesis of imidazolones reactionThe mechanisms of copper-catalyzed synthesis of imidazoloneswere studied at the B3LYP/6-311G（d, p） level, which we chose incopper-catalyzed synthesis of 4-Benzylidene-2-methyl-4,5-dihydro-1H-imidazol-5-one of the reaction mechanism research, and make adetailed theoretical calculation of the reaction mechanism. Throughin gas environment of the involved in the response of the reactants,products, intermediates and transition states for structureoptimization and the frequency calculation, the reaction of the tworeaction channels were found. After taking into account the solvationeffect of these two reaction channels, we know that the highestresponse potential barrier for the channel 1 is 37.64 kcal/mol, and thechannel 2 is 41.65 kcal/mol. So we identified that the channel 1 is themain channel of the reaction, the channel 2 for times channel.2. Theoretical study on the mechanism of copper-catalyzed C-Ccoupling synthesis of indoline-2, 3-diones reactionThe mechanisms of copper-catalyzed synthesis of indoline-2,3-diones were studied using the density functional theory method（DFT）, at the B3LYP/6-311G（d, p） level. Through the research weknow that:（1） Copper-catalyzed synthesis of indoline-2, 3-diones is a complexmulti-step reaction, there are two possible reaction mechanism. Theyare respectively Cu atom of CuCl₂on offense C₉H₉NO₂molecules ofthe C and O atoms. These two kinds of reaction mechanism can alsoproceed through two channels. （2） Based on the analysis of these two reaction paths potentialenergy surface and compare the relative energy of transition state ineach channel and the highest reaction barrier. We conclude that theCu atom of CuCl₂ on offense C₉H₉NO₂ molecules of the O atom is theoptimum reaction mechanism. And in this reaction mechanism, thechannel 3 is the main channel, the channel 4 for the times channel.Moreover, in Cu atom of CuCl₂ on offense C₉H₉NO₂ molecules of the Catom mechanism, the channel 2 is the main channel, the channel 1 isthe times channel.