Studies On Nitrile Involved Transition-Metal-Catalyzed Cascade Reactions For The Construction Quinoline-2,4-diones

Transition-metal-catalyzed cascade reactions have become one of the most powerful methods to construct organic compounds.In this field,numerous radical cascade reactions of N-arylacrylamides with different radical precursors have been developed,providing a new approach to access 3.3-disubstituted oxindoles.However,the cascade reactions of N-arylacrylamides for the synthesis of quinoline-2,4-diones have never been explored.This thesis describes several radical cascade reactions of o-cyanoarylacrylamides for the construction of various diversely functionalized quinoline-2,4-diones.This thesis contains the following three parts:1.Recent advances in the radical cascade reactions of N-arylacrylamides to give 3,3-disubstituted oxindoles were summarized in detail.The reactions are classified by the type of radical source,and introduced systematically.2.We presented a novel and facile Cu-catalyzed addition/cyclization cascade of o-cyanoarylacrylamides with hydrogen phosphoryl compounds,where the cyclization was accomplished by an intramolecular addition of the carbon radical to the nitrile.This reaction creates an opportunity to construct valuable phosphonylated quinoline-2,4(1H,3H)-diones.Preliminary mechanistic studies indicate that the reaction might involve a radical process.3.We descried radical addition/cyclization cascade of o-cyanoarylacrylamides with acyl radicals using different acyl radicals resources,such as a-keto acids,aldehydes and alcohols.Several reaction systems.a-keto acids/AgNO3/K2S2O8,aldehydes/K2S2O8/benzoic acid and alcohols/FeCl2/tert-butyl hydroperoxide,have been developed to construct carbonyl-containing quinoline-2,4(1H,3H)-diones.