Nickel-Catalyzed Activation And Transformation Of C-O And C-N Bonds

This paper describes a series of nickel-catalyzed activation and transformation of C-O bonds and C-N bonds.Chapter 1 describes nickel-catalyzed a-arylation of ketones with aryl 2-pyridyl ethers as the arylating reagents.In this reaction the CAr-OPy bond can be selectively cleaved.Activated,unactivated and deactivated aryl 2-pyridyl ethers suit for the coupling,and various functional groups on the aromatic rings are tolerated.The ke-tones used in this transformation include propiophenone and acetophenone deriva-tives.The β-H in the ketones can be tolerated and monoarylation of acetophenone derivatives can be successfully carried out.This methodology would provide a val-uable complement to the a-arylation of ketones and enrich the utilization of phenols in synthetic chemistry.Chapter 2 describes nickel-catalyzed amination of aryl 2-pyridyl ethers through cleavage of the C-OPy bond.The method displays a broad scope of substrates in-cluding electron-rich and electron-poor aryl 2-pyridyl ethers and various amines.The reaction gives reasonable to excellent yields and exhibits good compatibility of func-tional groups.This methodology is a valuable complement to Buchwald-Hartwig reaction involving phenol derivatives.Chapter 3 describes the nickel-catalyzed hydrogenation of aryl and benzyl 2-pyridyl ethers through cleavage of the C-OPy bond.The reaction gives mostly ex-cellent yields,suits for a broad substrate scope and exhibits good functional group compatibility.This methodology would provide an effective way to reductive deox-ygenation and a widely applied process in the directed functionalization of phenols and benzyl alcohols.Chapter 4 describes nickel-catalyzed a-arylation of ketones with aryltrime-thylammonium triflates as the arylating reagents.Activated,unactivated and deac-tivated aryltrimethylammonium triflates suit for the coupling.The ketones used in this transformation include propiophenone,butyrophenone and acetophenone deriva-tives as well as cyclohexanone.In the reaction β-H in ketones can be tolerated and monoarylation of acetophenone derivatives can be carried out.This methodology would provide a valuable complement to the a-arylation of ketones and enrich the utilization of aromatic amines in synthetic chemistry.