Design,Synthesis And Application Study Of Gold Complexes

Gold catalyst has attracted significant attention for its unique catalytic advantages,which is considered to be one of the most promising areas in organic synthesis.However,gold catalysis has poor stability and easily decomposes,In addition,the generated floc AgX accelerated the decomposition of active gold catalysts.Triazole ligand is easy to form relatively stable metal feedback ? bond because of strong ?-donor and lower LUMO,and could enhance the stability of gold complexes with strong coordination ability.Therefore,our work was foucsed on the design,synthesis and application study of gold complexes based on triazole skeleton ligands.(1)First,triazole acetyl skeleton gold complexes were designed through the reaction of triazole acetyl ligand and inorganic gold salts,and the structure was determined by divce characterization.Thermogravimetric curves of gold complexes showed that the stability of gold complex had been greatly improved.Catalytic performance tests showed that the complex had catalytic activity in Meyer–Schuster rearrangement of propargyl alcohols.(2)Second,on the basis of triazole acetyl ligand,triazole alanine ligand was synthesized by introducing natural alanine molecules,then triazole alanine skeleton gold complex was designed with this ligand.TG experiment showed that the gold complex exhibited much greater thermal stability.Besides,the complex was applied to allene synthesis,it was found that the in-situ formed catalyst had the same catalytic activity compared with the previously prepared catalyst.Therefore,we adopt in-situ formation of catalyst for substrate expansion experiments,and found that the complex had a very good substrate adaptability.At the same time,alanine triazole gold complex had exhibited excellent potential as a means to catalyze borrowing hydrogen of alcohols.(3)Compared with triazole,pyridine also showed a good coordination ability,in order to obtain more stable gold complexes,and to compare the stability of pyridine and triazole on gold,pyridine triazole gold(I)complex was synthesized and characterized by 1H NMR,13 C NMR and X-Ray,the result revealed that triazole was much easier to coordinate with gold and greatly enhanced its thermal stability.Thermal stability experiments showed that the complex had high stability in air and toluene solvents.In addition,the rearrangement reaction of propargyl ester/propargyl vinyl ether showed that the complex had good catalytic activity.(4)Then,combined with gold(?)four coordination way,pyridine triazole gold(?)complex was successfully synthesized by using this ligand and the structure of this complex was also characterized and determined.Thermal stability experiment and catalytic activity experiment showed that the complex had excellent stability and effective reactivity for a-haloenones with moderate to good yields.At the same time,with this new gold(?)catalytic system,the challenging a-chloroenone substrates were synthesized for the first time,(5)Last,triazole ester gold complex was prepared by using triazole ester ligand in high yields.The structures of the complex was characterized by the related instruments,and the thermal stability was analyzed by thermogravimetry.Subsequently,the complex was applied to N-alkylation of primary amines.The experimental results showed that the complex had good catalytic activity for the hydrogenation.