Synthesis Of Copper Corrole And Its Application In Cross-Dehydrogenative Coupling Reaction

Finding ways to build C-X（X=C,O,N）bonds has become a hot research direction in the chemical industry in the past few years.Among many methods,the direct activation coupling of C-H bonds is the most effective and environmentally friendly method,because it reduces the use of organohalides,pseudohalides or organometallic reagents.Scientists have explored a new method to directly construct C-X bonds through the coupling of activated C-H bonds with substrates under aerobic conditions through metal catalysis,which is cross dehydrogenation coupling（CDC）reaction.Coupling of C（sp³）-H substrate with carboxylic acid is a convenient method for preparing esters.Many catalysts such as Bu₄NI,iron and copper have been successfully applied to the oxidative coupling of carboxylic acid and cyclic ether,the catalyst loading is generally 20 mol%.In recent years,5,10,15,20-tetra（ethoxycarbonyl）porphyrin copper（II）（Cu TECP）and5,10,15,20-tetra（ethoxycarbonyl）porphyrin Iron（III）chloride（Fe TECPCl）have successfully used to catalyze the esterification reaction of 1,4-dioxane C（sp³）-H with carboxylic acid.Corrole is similar to porphyrin in structure and properties,this thesis mainly studied the CDC esterification reaction of 1,4-dioxane C（sp³）–H with carboxylic acid derivatives catalyzed by metal corrole.The main contents are as follows:1.In this thesis,5,10,15-tris（pentafluorophenyl）corrole(F₁₅C),5,15-bis（pentafluorophenyl）-10-（phenyl）corrole(F₁₀C),5,15-bis（phenyl）-10-（pentafluorophenyl）corrole（F₅C）,5,10,15-tris（phenyl）corrole（F₀C）and the corresponding copper complexes F_1C5-Cu,F₁₀C-Cu,F₅C-Cu and F₀C-Cu were synthesized,these compounds have characterized by characterization methods such as ultraviolet,nuclear magnetic and X-single crystal diffraction.2.In this thesis,corrole complexes was firstly used to catalyze the CDC esterification of1,4-dioxane C（sp³）–H with carboxylic acid derivatives.Among four metal corrole complexes catalysts,5,10,15-tris（pentafluorophenyl）cooper corrole showed the best catalytic activity.Then this paper investigated the influence of the equivalent weight of the catalyst,the type of oxidant,the reaction temperature and the concentration of the reactants on the catalytic reaction.The best reaction conditions are:benzoic acid（0.5 mmol）,1,4-dioxane（2 ml）,catalyst F₁₅C-Cu（0.5 mol%）,react at 120℃for 12 h.Under these conditions,our final separation yield reached 96%.On the basis of the above optimal conditions,the substrate of this cross-coupling reaction was expanded.Among the more than 30 kinds of substrates,both electron-donating benzoic acid and electron-withdrawing benzoic acid have good adaptability.It shows that F₁₅Cu catalyzes the high efficiency of dehydrogenation cross-coupling reaction,and could obtain the target product with a higher yield.3.When the equivalent weight of the 5,10,15-tris（pentafluorophenyl）corrolato cooper catalyst decrease to one ten thousandth,the yield of the reaction can still reach 84%,indicating that the catalyst has a higher industrial application value.In addition,in order to study the mechanism of the reaction,free radical capture experiment,kinetic isotope effect experiment and electron paramagnetic resonance（EPR）experiment were conducted.These experiments proved that the reaction is a reaction of free radical mechanism.