Synthesis Of MCM-41-supported Bidentate Nitrogen Copper Complexes And Their Applications In Carbon-Carbon Bond And Carbon-Heteroatom Bond Formation Reaction

This dissertation consists of two parts:Part one: Dinitrogen-functionalized MCM-41anchored copper complexes wereconveniently prepared from commercially available3-（2-aminoethylamino）-propyltrimethoxysilane via immobilization on MCM-41, followed by reacting withcopper salts such as CuI, CuSO₄, CuCl or Cu（OAc）₂. These supported coppercomplexes were characterized by XRD, ICP and elemental analysis.Part two: We investigated the homo-and heterocoupling reactions of terminalalkynes catalyzed by MCM-41-2N-CuI. It was found that the oxidative homo-andheterocoupling of terminal alkynes proceeded very smoothly in the presence of acatalytic amount of MCM-41-2N-CuI to give the corresponding homo-andheterocoupling products in good to excellent yields under air atmosphere at roomtemeprature using CH₂Cl₂as solvent and piperidine as base. This heterogeneouscopper catalyst exhibited high catalytic activity and can be recovered and recycled bya simple filtration of the reaction solution and used for at least10consecutive trialswithout any decreases in activity. The N-arylation reaction of various indoles witharyl iodides proceeded very smoothly in the presence of a catalytic amount ofMCM-41-2N-CuI in good to excellent yields at110℃using K₃PO₄as base andtoluene as solvent. The less reactive aryl bromides and aryl chlorides also reacted withindoles readily in good yields. Electronic effect and the steric effect of substituents onthe aryl ring have a important effect on the rate of the reaction, but the reactionproceeded smoothly. It was found that MCM-41-2N-CuSO₄can efficiently catalyzethe tandem reactions of2-haloanilines with isothiocyanates under air. A variety of2-aminobenzothiazoles was synthesized in good to excellent yields. The novelsupported bidentate nitrogen copper catalyst can be easily recovered by simplefiltration and reused10times without any decreases in activity. MCM-41supportedbidentate nitrogen cuprous chlorid catalyst（MCM-41-2N-CuCl） was perpared byreacting CuCl with MCM-41-2N without silylation with Me3SiCl in DMF at roomtemperature. The reaction of variety of aryl iodides with KSCN proceeded smoothly in the presence of MCM-41-2N-CuCl to give the corresponding diaryl sulfides ingood yields under argon atmosphere at130℃using neat H2O as solvent and Cs2CO3as base. This heterogeneous copper catalyst exhibited good catalytic activity and canbe recovered and recycled by a simple filtration of the reaction solution and used forat least10consecutive trials without any decreases in activity.We have designed and synthesied of several dinitrogen-functionalized MCM-41anchored copper complexes, and applied them to the carbon-carbon andcarbon-hyberoation bond formation reactions,. providing convenient, practical greenroutes for the synthesis of1,3-diynes, N-arylated indoles,2-aminobenzothiazoles, anddiaryl sulfides.