Transition-metal-catalyzed Carbonylation Of Benzylic Quaternary Ammonium Salts And Reductive Cross-coupling Reaction

The transition-metal-catalyzed cross-coupling reaction is highly efficient and selective method for the construction of carbon-carbon,carbon-hetero bonds,and is also one of the hotspots in the research of organic synthetic chemistry.This method has wide range of applications in scientific research and industrial production.Palladium and nickel are the most common transition metals,their catalyzed cross-coupling reactions are the most widely used and have significant advantages.In recent years,palladium-catalyzed carbonylation reaction to esterify of the Sp~3(C)-X bond activation is an important route for the synthesis of alkyl esters.Alkoxycarbonylation usually needs to be performed under high temperature or high pressure conditions.Therefore,to development a mild and efficient method of Alkoxycarbonylation with Sp~3(C)-X bond activation has great value and significance.In addition,transition-metal-catalyzed reductive coupling reactions have also become important methods for the construction of C-C bonds.However,these cross-coupling reactions generally require the participation of metal reduction reagents.These reactive metals usually need to be preactivated and cannot be recycled.In this text,we initially summarize the palladium catalyzed carbonylation of Sp~3(C)-X bond and the development of transition metal-catalyzed reductive coupling reactions.Afterwards,we separately put forward scientific questions on the two aspects research,analyze and solve these problem subsequently.This text mainly studies on the following two major contents:1.we have developed an palladium-catalyzed alkoxycarbonylation of benzyl quaternary ammonium via C-N bond cleavage under atmosphere pressure.The reaction is simple and has a wide range of substrates.2.Visible-light driven,Ni/Ir co-catalyzed reductive cross-coupling reaction of vinyl bromides with unactivated tertiary bromides has been reported,this reaction avoids the use of metal reducing reagents,and has great potential application for the synthesis of quaternary carbon center compounds.