Study On Cross-dehydrogenative Coupling Reaction Of Allylic C(sp~3)-H Bonds With Carboxylic Acids Catalyzed By Copper Corroles

C-H bond activation is an important strategy for the formation of C-C bond and C-X（X=heteroatom）bond in organic synthesis.In various methods for constructing C-C bond and C-X bond,a direct coupling of two C-H bonds or one C-H bond and one X-H bond catalyzed by transition metal is called cross-dehydrogenative coupling（CDC）reaction,which has attracted wide attention of researchers.Allyl ester is a key motif in organic synthesis.The direct application of CDC strategy to the synthesis of allyl esters from allyl substrates with acids is more atom economical than the C-H oxidative esterification between the precursors of acids（aldehydes,arylmethanes,olefins or alkynes）with olefins.In order to study the catalytic effects of copper corrole complexes on this reaction,the CDC esterification of allyl C（sp³）-H with carboxylic acid catalyzed by copper corrole was investigated.The main contents of this dissertation are as follows:1.Free-base corrole H₃TPC and H₃TPFC,and their metal complexes（Cu TPC,Cu TPFC,Mn TPFC and Co TPFC·PPh₃）were synthesized respectively by one-pot method and two-step method at room temperature,which were characterized by UV-Vis and NMR.2.The catalytic effects of three corrole complexes（Cu TPFC,Mn TPFC and Co TPFC·PPh₃）on the oxidative dehydrogenative coupling reaction of acids with allylic C（sp³）-H providing esters were compared.It was found that the catalytic effect of copper corrole was far better than that of manganese and cobalt.Meanwhile,the catalytic activities of copper corroles with different fluoride content was compared.It was found that the catalytic effect of the metalocorrole with higher fluoride content was slightly better than that without fluoride.After screening the reaction conditions,benzoic acid（0.3 mmol）,cyclohexene（3 mmol）,Cu TPFC（0.1 mol%,vs benzoic acid）,DTBP（0.6 mmol）,and DCE（1 m L）at 120℃for 12 hours was chosen.Under this condition,the esterification product 2-cyclohexene benzoate was isolated95%yield.3.Based on the results mentioned above,33 substrates were expanded for the reation,which proved the high efficiency of Cu TPFC in catalyzing CDC reaction.Both electron-withdrawing and electron-donating substrates were well adapted to the reaction process obtaining the desired products at medium to high yields.In addition,the regioselectivities of asymmetric olefins and the different selectivities of terminal and internal alkenes were investigated.Finally,the CDC reaction of allyl C（sp³）-H bonds with acids catalyzed by Cu TPFC was found carring out through the radical mechanism.