Transition-Metal-Catalyzed Synthesis Of ?,?-Unsaturated Nitriles

?,?-Unsaturatednitriles are a especially useful class of cyanides in synthetic chemistry.They are not only important compounds in dyes and perfumes but also key structural units in various potential medicinal drugs.In this thesis,we mainly focus on the new approach to the synthesis of?,?-Unsaturatednitriles through the scientific and systematic exploration.We divided our work into two parts.For the first part,wedisclosed the Cu/Ni-catalyzed direct coupling of alkene and acetonitrile to provide?,?-Unsaturatednitriles.We used1,1-diphenylethylene as model substrate,by screening conditions,finally we developed a new strategy for the synthesis of?,?-Unsaturatednitrilesthroughthe cross dehydrogenative coupling(CDC)reaction of aceto-nitrile sp³ C-H bondand alkenes sp² C-H bond in the presence of copper and nickel catalystsas cooperative catalysts,1,10-Phen as ligand,TBPB as oxidant.Acetonitrile,through C(sp³)-H activation,as a effencient cyanomethyl reagent,is low-toxicity?atom-economy and is in line with the concept of green chemistry.For substrates,all kinds of 1,1-disubstitued alkenes show high compatibility underthis catalytic system.The transformations of products show the potential applications of this method.A series of mechanistic studies reveala radicalmechanism is included.For the second part,we foused on the addition of alkenes and bromoacetonitrile.We chosed 2-Vinylnaphthaleneas a starting material,bromoacetonitrile as the cyanomethyl reagent,after optimizing,we reported a simple and efficient catalytic system to synthesize desired?,?-Unsaturatednitriles by using Cu Cl as a catalyst and K₂CO₃as base.All kinds of 1,1-substituented alkenes can undergo the desired reactions and furnish the corresponding products in high yields,which can be regarded as a complement to the last reaction at the same time.