Supramolecular Catalytic Properties Of Hemi-cucurbit-like Macrocyclic Compounds

An effective method for the synthesis of dibenzo[a,j]phenazine compounds by Hemi Q-catalyzed oxidative dimerization of 2-arylamine is established by investigating the dimerization reaction of 2-naphthylamine in the presence of Hemi Q[6].The dimerization is achieved through the catalytic action of Hemi Q[6] in an acidic environment.Kinetic constants and activation energies have been calculated through UV/Vis spectrophotometric investigations using different amounts of Hemi Q[6],whereby the reactivity was found to be related to the electron densities of the substrates.A possible mechanism involving host–guest interaction between a2-arylaminium salt and Hemi Q[6] through hydrogen-bonding is proposed.The transformation of 2-arylamines to dibenzo[a,j]phenazines in the presence of Hemi Q[6]suggests that such supramolecular catalysis is effective for such constructions.The catalytic oxidation characteristics of hemicucurbituril give us inspiration to develop the electrocatalytic organic synthesis of hemicucurbituril.Macrocyclic compound [O]-Chiral Mulifarene [3,2,1](O-CMF)with electrochemical chiral recognition ability was modified on glassy carbon electrode to construct chiral electrode.Asymmetric electroreduction of acetophenone was used to mildly synthesize 1-phenylethanol with good yield and ee value.the reaction also had a good conversion rate.Electrochemical impedance analysis showed that the modified electrode was successfully constructed.The electrochemical reduction behavior of acetophenone was studied by cyclic voltammetry,and the possibility of the reaction was determined.The effects of electrolysis method,post-treatment method,solvent type,supporting electrolyte type,amount of modified macrocyclic compounds,water content,p H value,electrolysis potential and modification of different macrocyclic compounds on the electroreduction of acetophenone were investigated.After electrolysis under the optimal screening conditions,1-phenylethanol with a yield of40.5% was obtained.1-phenylethanol was mainly S-configuration,and its ee value reached 38.5%.Alkaloids were used as chiral catalysts,which could induce chirality in the electrolyte.It cooperated with the established O-CMF modified chiral electrode to conduct electroreduction of acetophenone and further improve the ee value of 1-phenylethanol.The cyclic voltammetric behavior of acetophenone in the presence of different alkaloids was investigated at the chiral electrode.It was proved that hydrochloric acid alkaloids can further improve the peak current of acetophenone,and can also cooperate with the chiral electrode to catalyze acetophenone.In the presence of QN-HCl,1-phenylethanol with yield of 46.8%,conversion rate of 93.9% and ee value of 46.5% was obtained by asymmetric electroreduction of acetophenone with chiral electrode.This thesis provides that the use of supramolecular Hemi Q[6] to specifically and efficiently catalyze the synthesis of dibenzo[a,j]phenazine compounds had a high product yield,which was a very good method so far.In this thesis,[O]-Chiral Mulifarene supramolecules with chiral cavities were applied in the field of asymmetric electrosynthesis,which broadened the research scope of supramolecules in electrochemical catalysis.