Copper-catalyzed Oxidative Difunctionalization Of Alkenes For The Synthesis Of ?-lactone And ?-lactam

The carbon-carbon double bond is a kind of very important organic functional groups in organic chemistry.Its high reaction reactivity can achieve many reactions,such as addition reaction,annulation reaction,oxidation reaction and reductive reaction,for the structural complex organic compounds.Moreover,the C=C unsaturated bond is widely existed in drug molecules and natural products.Therefore,development of new methods for the transformations of the C=C bonds would be desirable,which might improve the biological activity,biological compatibility and biological utilization of many natural products,drug molecules,and drug molecule precursors by deriving and modifing teir highly active and area of pharmacology and efficacy of functional groups,and then make the new modified drug molecules more efficient,safety,and specificity in the practical applications.Difunctionalization of alkenes enables the introduction of two different functional group across the C=C bond in the single reaction to access difunctionalized molecules.Difunctionalization of alkenes exhibits many excellent advantages in organic synthesis,such as high selectivity,wide range of reaction substrates,and execellent compatibility of functional groups.For these reasons,the alkene difunctionalization reactions have attract much attention of many chemical researchers for selectively transforming the C=C bonds into diverse highly bioactive and medicinal valuable compounds,which may improve their applications in materials and pharmaceuticals.Through the continuous innovation of scientists,the transition metal catalyzed difunctionalization reaction of olefins not only realized the diversification of the catalyst species,but also introduced the chiral ligands in the metal catalyst system to realize the selective functional functionalization of olefins,Which laid a solid theoretical foundation for the subsequent application of bifunctional reactions.This dissertation mainly focuses on the copper-catalyzed oxidative difunctionalization of alkenes for the synthesis of y-lactams and y-lactones.This dissertation includes the following contents:(1)Firstly,recent progress in the difunctionalization reactions of olefins catalyzed by transition metals has been reviewed in detail.We discussed three types of olefin difunctionalization,including(i)advances in palladium-catalyzed difunctionalization of Unsaturated Hydrocarbons,(ii)advances in copper-catalyzed difunctionalization of Unsaturated Hydrocarbons,and(iii)advances in the difunctionalization of olefins using the other transition metals.Moreover,the mechanisms of olefin difunctionalization reactions were also discussed.(2)In the second chapter,copper-catalyzed oxidative radical two-component[3+2]annulation reaction of olefins with a-bromoalkyl was presented with the aid of Ag2CO3 as the oxidant.The reaction provides a simple and practical route to producing a variety of high bioactive y-lactone compounds by the construction of two chemical bonds,a C-C bond and a C-O bond,in one pot.(3)In the third chapter,a new copper-catalyzed tandem annulation of alkenes with a-bromoalkyl esters and primary amines for producing polysubstituted pyrrolidin-2-ones has been developed.The reaction allows the formation of three new chemical bonds,one C-C bond and two C-N bonds,in a single reaction,and represents the first three-component difunctionalization of alkenes for the synthesis of pyrrolidin-2-ones involving[2+2+1]annulation.The reaction conditions are mild,reaction efficiency is high,operation is simple and the substrate adaptability is wide.By using the cheap and efficient catalytic system,a series of bioactive y-lactam which in the treatment of epilepsy,AIDS,neurodegenerative Disease,allergic diseases and depression and other aspects have shown a high biological activity is synthesized.