Transition-Metal-Catalyzed Transformation Of C-O And C-N Bonds

In this paper,transition-metal-catalyzed transformation of aryl and alkyl C-O bonds as well as aryl C-N bonds are described.Chapter 1 introduces the cross-coupling reaction between aryl 2-pyridyl ether and silyzinc reagent catalyzed by NiCl2(PCy3)2,which realizes the selective cleavage of C-OPy bond under mild conditions and generates the corresponding silylated arenes.The method suits for a wide scope of aryl 2-pyridyl ethers including those with electron-poor and electron-rich aryl groups and nitrogen-containing heteroaryl groups as well as various phenylsilylzinc reagents.This method can also be applied to a series of ortho-substituded aryl 2-pyridyl ethers,which provides a new way for the transformation of OPy group after OPy-directed ortho C-H functionalization.This reaction also provides a new method for the synthesis of silylated arenes.Chapter 2 presents nickel-catalyzed cross coupling reaction of aryl 2-pyridyl ether with alkylmagnesium halides,which can selectively cleave Caryl-O bonds and construct Csp2-Csp3 bonds.A range of functional groups on the aromatic rings including CO2R,OMe,OPh and CONEt2 groups were tolerated.In most cases,excellent yields can be achieved.The preliminary mechanism study shows that the reaction may proceed via a free radical process.Chapter 3 describes the reaction of aryldiazonium tetrafluoroborates with organozinc reagents catalyzed by Pd(OAc)2/PPh3.Both electron rich and electron poor aryldiazonium salts are good electrophilic reagents.Aryl,methyl and vinyl zinc reagents can be used as the nucleophiles.The reaction can selectively occur on the Caryl-N bond when the compound has C-Cl or C-Br bond.Chapter 4 is about ?-alkylation of arylacetonitriles with alcohols catalyzed by[IrCp*Cl2]2.This protocol applies to a wide range of alcohols and nitriles including secondary and primary alcohols,and aryl,naphthyl,and heteroaryl acetonitriles,resulting in the corresponding alkylated products in medium to excellent yields.Functional groups on the arylacetonitriles including OMe,NHCOR,acetal groups as well as heterocycles can be tolerated.This study is a valuable complement to the ?-alkylation of nitriles using alcohols.