Studies On Copper-catalyzed Difunctionalization Of Carbon-carbon Multiple Bonds

Carbon-carbon,carbon-hydrogen,carbon-oxygen,and carbon-nitrogen bonds are the most basic chemical bonds to construct structures of organic molecules.Undoubtedly,the construction of these chemical bonds is the central task of organic synthesis.Copper-catalyzed difunctionalizations of carbon-carbon multiple bonds have proven to be efficient approaches to construct carbon-carbon and carbon-heteroatom bonds.Copper-catalyzed difunctionalization of carbon-carbon multiple bonds involving radical addition reactions of various carbon-centered or even heteroatom-centered radicals is one of important reaction types among copper-catalyzed difunctionalization reactions.These reations usually have advantages of easy availability of copper catalysts,atom-economy and step-economy,and rapid construction of molecular complexity and diversity.The dissertation is mainly divided into four parts:（1）In the first chapter,a brief introduction of recent progress in copper-catalyzed difunctionalizations of carbon-carbon multiple bonds was reviewed.It was organized based on different types of carbon-carbon multiple bonds,such as double bonds and triple bonds.（2）In the second chapter,the synthesis ofα-trifluoromethyl enones via copper-catalyzed trifluoromethylation of aryl propargylic cyclobutanyl alcohols with Togni’s reagent was studied.The reation provided an efficient approach to deliver a range ofα-CF₃ enone products with moderate yields by simply using copper salts as catalysts,Togni’s regent as CF₃ source,and readily accessible substituted aryl propargylic cyclobutanyl alcohols as substrates.（3）In the third chapter,an efficient construction of 5-arylbenzofluorenones involving Cu（I）-based photosensitizer-catalyzed tandem radical addition/annulation of1,6-enynes was studied.The reation utilized aryl diazonium salts as aryl radical sources to deliver 5-arylbenzofluorenones catalyzed by P/N-heteroleptic Cu（I）-based photosensitizer under photoredox catalysis conditions.The reaction has advantages of mild reaction conditions,simple operation and broad substrate scope.（4）In the fourth chapter,we summarized the research contents of this dissertation,and proposed suggestions for further studies based on the present outcomes.