Palladium/Ruthenium-Catalyzed C-H Bond Activation And Asymmetric Reactions

Transitional metal-catalyzed C-H bond activation is one of the important methods to form new chemical bonds,and it is also a hot topic of orgaometallic chemistry today.This thesis enriches the research of palladium-catalyzed C-H bond functionaliztion for the synthesis of planar chiral ferrocenyl compounds and diarylphosphoxypyridine derivatives.Firstly,palladium-catalyzed the intramolecular asymmetric C-H bond arylation had been achieved for the synthesis of planar chiral ferrocenyl thiophenes compounds.Secondly,the ferrocenyl benzodiazepine sulfone compounds were constructed by the C-H bond arylation of ferrocenyl sulfone compouds using norbornene as a transient mediator.Palladium-catalyzed C-H silylation had been developed to synthesis disilylated ferrocenyl derivatives assisted by hexamethyldisilane.Finally,Pyridinyl-directed ruthenium-catalyzed ortho-C-H bond arylation of aryl phosphorus oxide compounds had been developed for the synthesis of diarylphosphoxypyridine derivatives.This thesis is mainly includes two chapters.The first chapter introduces the recent advances in the field of palladium-or ruthenium-catalyzed C-H bond functionalization.The experimental research parts are as follows:1.Palladium-catalyzed intramolecular asymmetry C-H bond activation for the synthesis of planar chiral benzothiophene-fused ferrocenesPalladium-catalyzed the intramolecular asymmetric C-H bond cyclarization of ortho bromoaryl ferrocenyl sulfur compounds had been developed.Stereoselectivity can be effectively controlled by diphosphine ligands((R)-Segphos)and the chiral ferrocenyl thiophenes compounds were synthesized in high enantioselectivities(94-99%ee).Planar chiral compounds containing sulfur or phosphor mioeties had been used in the asymmetric reaction.2.Palladium-catalyzed intramolecular asymmetry C-H bond activation for the synthesis of planar chiral ferrocenyl thiophenes sulfone compoundsPalladium-catalyzed the intramolecular C-H functionalization/cyclization of ferrocenyl sulfone compounds had been developed for the synthesis of planar chiral ferrocenyl benzothiophene sulfone compounds in high yield(97%)and excellent enantioselectivity(96%).Disubstituted ferrocenyl sulfone compounds are also compatible.3.Palladium-catalyzed the activation of intermolecular C-H bond for the synthesis of ferrocenyl benzodiazepine sulfone compoundsPalladium-catalyzed the intermolecular Catellani-type arylation of ferrocenyl sulfone compounds via double C-H bond activation had been developed.Five-membered ring products were generated in the presence of electron-rich aromatics,possibly because of the oxidation addition of palladium and ortho-bromo phenyl ferrocenyl sulfone compounds.Palladium preferentially cut C-I bond to selectively generate a seven-membered ring product in high yields with 2-iodobenzotrifluoride.4.Palladium(Ⅱ/Ⅳ)-catalyzed the activation of intermolecular C-H bond for synthesis of disilylated ferrocenyl compoundsPd(Ⅱ/Ⅳ)-catalyzed C-H bond disilylation of(2-iodophenyl)-ferrocene and hexamethyldisilane had been developed.The C-I bond and C-H bond were cut off successively by using palladium catalyst and the disilylated ferrocenyl compounds were successfully synthesized in high yield in the presence of monophosphorus ligands.In addition,lower ee products(14%)were achieved with Taddol-type ligands.5.Ruthenium catalyzed the ortho-C-H bond arylation for the synthesis of diarylphosphoxypyridine derivativesPhosphine ligands containing 2-pyridine moiety play an essential role in catalytic reaction,which can be used as bidentate ligand or monocoordinated ligand.Pyridinyl-directed ruthenium-catalyzed ortho-C-H bond arylation for the synthesis of diarylphosphoxypyridine derivatives had been developed and good reaction results were achieved(up to 98%yield).This approach provides a new way for the preparation of new phosphine ligands.