Study On C-C Bond Formation Reaction Based On C-O Bond Cleavage And C-H Bond Functionalization

This thesis consists of two parts,including the C-C bond reductive coupling reaction based on C-O bond cleavage and the C-C bond formation reaction based on CH bond functionalization.The first part is about the C-C bond reductive coupling reaction based on C-O bond cleavage.(i)Nickel-catalyzed reductive coupling reaction of allyl alcohols with aryl chlorides and aryl/allyl trifluoromethanesulfonates were developed,achieving allylated arenes or alkenes.The method shows high regioselectivity,E/Z selectivity and good compatibility of functional groups.The reaction of 1-and 3-aryl substituted allyl alcohols gave linear coupling product with E-configurated double bonds.This protocol provides a new approach for synthesis of the compounds containing allyl group moiety.(ii)Nickel-catalyzed reduction coupling reaction of alkyl methanesulfonates with 2pyridyl arylcarboxylates was developed,affording alkyl aryl ketones.This method exhibits a wide range of substrates and good compatibility of functional groups.Both primary and secondary alcohols derived methanesulfonate esters can be used for this conversion;various functional groups on the carbon chain of fatty alcohols including C-C double bonds,C-C triple bonds,Cl,COOMe,and OC(O)Ar groups,as well as Br,F,CF3,and OMe groups on the phenyl rings of aromatic alcohols were tolerated.The second part is about the C-C bond formation reaction based on C-H bond functionalization.(i)Palladium/copper-catalyzed decarbonylation coupling reaction of terminal alkynes with 2-pyridyl arylcarboxylates was developed,achieving disubstituted alkynes in medium to excellent yields.This provides a new path for the synthesis of internal alkynes.(ii)Rhodium-catalyzed C-H acylation reactions of aryl amides with diphenylphosphines was realized,achieving a range of acylated arylphosphines.This method shows a wide scope of substrates and good compatibility of functional groups.(iii)With 2-vinyl cycloamines as allylation reagents,rutheniumcatalyzed C-H allylation of 2-arylpyridines was developed.This reaction introduces allyl and amino groups into aromatic molecules at once,providing a method for the synthesis of more diverse multifunctional molecules.