Preparation Of AOFs Metal Complex Catalyst And Its Catalytic Coupling Reaction Of Terminal Acetylene With Sp3-C

Carbon-carbon triple bond is one of the most important structural units in organic synthesis chemistry.The coupling reaction of terminal alkynes with sp3-C catalyzed by transition metals is one of the most effective methods to synthesize carbon-carbon triple bond.In this paper,amidoxime fibers with coordination ability were selected as the carrier for supporting metal ions,and the metal ion and fiber were firmly combined by chemical coordination reaction to prepare a fiber metal complex catalyst.Then metal catalysts were used in the coupling reaction of Csp-Csp3,including the coupling reaction of terminal alkynes with C(sp3)-Br,the coupling reaction of terminal alkynes with C(sp3)-O,and the coupling reaction of terminal alkynes with C(sp3)-H.The catalysts were characterized and analyzed,and the combination of metal ions and fiber was studied.The process conditions of the reaction system were optimized and the substrate derivatives were explored.The research results are shown as follows:(1)Metal complex catalysts were prepared by the reaction of modified polyacrylonitrile-amidoxime fibers with metal ions,and then the morphology and valence of the catalysts were characterized.(2)Fiber-supported metal complex catalysts were used to catalyze the cross-coupling reaction of phenylacetylene and C(sp3)-X.The coupling reaction of phenylacetylene and bromopropene was used as the template reaction.The effects of different kinds of catalysts on the coupling reaction were investigated.The results showed that the target product obtained by Pd(II)/Cu(II)-AOFs catalyst had the best effect.By optimizing the experimental conditions,the optimal reaction conditions were obtained:The catalyst is Pd(?)/Cu(?)-AOFs(0.5 mol%,10 mol%,0.1 g),the solvent is EtOH/H2O(3:1),the base is K2CO3,the reaction temperature is 70?,and the reaction time is 3 h,78%of the cross-coupling product can be obtained.At the same time,the catalyst has a good catalytic effect after repeated use for 5 times,the catalyst has a certain substrate tolerance and the same catalytic effect for aliphatic terminal alkynes.(3)Fiber-supported metal complex catalysts were used to catalyze the cross-coupling reaction of phenylacetylene and C(sp3)-O.The coupling reaction of phenylacetylene and diphenylmethanol was catalyzed by Fe(III)-AOFs.The optimum conditions were obtained by optimizing the experimental conditions:The catalyst is Fe(?)-AOFs(6 mol%,0.1 g),solvent is THF,base is Et3N,reaction temperature is 70 ?,reaction time is 5h,and 69%cross-coupling products were obtained.At the same time,the catalyst has a certain substrate tolerance,and has the same catalytic effect for terminal alkynes with different substituents.Pd(?)-AOFs and CuCl were selected to catalyze the coupling reaction of phenylacetylene with N,N-dimethylformamide dimethyl acetal.The optimum conditions were obtained by optimizing the experimental conditions:Pd(?)-AOFs,CuCl(0.6 mol%,0.1 g,8 mol%),NMP as base,DCE as solvent,reaction temperature is 80 ?,reaction time is 5 h,and 63%cross-coupling products were obtained.The catalyst has a certain substrate tolerance.(4)Fiber supported metal complex catalysts were used to catalyze the cross-dehydrogenation coupling reaction of phenylacetylene and C(sp3)-H.Copper(II)-AOFs catalyst catalyzes the coupling reaction of terminal alkynes with N,N-dimethylaniline.Through optimizing the experimental conditions,the optimum conditions are obtained:catalyst is Cu(II)-AOFs,solvent is toluene,base is Et3N,oxidant is tBuOH,reaction temperature is 100 ?,reaction time is 5h,and 43%cross-coupling products can be obtained.