The C-H Bonds Amination Based On Azodicarboxylate

The construction of C-N bonds has always been a hot and difficult point in synthetic chemistry.The direct amination of C-H bonds does not require pre-activation of substrates,so it is widely used and draws many chemists'interest.Azodicarboxylate is a kind of nitrogen sources with strong electrophilicity,and can be used in many chemical reactions.This dissertation focuses on the amination of C-H bonds with azodicarboxylates as nitrogen source,and we used a variety of methods to solve the challenging chemical problems at present.This dissertation mainly includes the following three parts:Part ?:The C-H bonds amination is successfully achieved for the first time on methylene using amide as the direting group,palladium as the catalyst and azodicarboxylate as the nitrogen source.The reaction conditions are simple,with a wide range of substrates.A variety of?-amino acid derivatives can be easily obtained from the products through reduction and acidolysis.In addition,a series of products with specific structures can lead to new chiral diamine catalysts,which are successfully carried out in enantioselective reactions.Part ?:A simple and efficient transition metal-catalyzed C-H amination with azodicarboxylates has been developed.Under silver catalysis,the amide substrates undergo regioselective C-H amination at C5-position of the quinoline.Conversely,with palladium as the catalyst,the reaction gave?-C(sp~3)-H amidation products via the activation of methylene C(sp~3)-H bonds.Mechanistic studies suggested that the single-electron-transfer and organometallic mechanism pathways gave rise to these surprising and distinct outcomes.Part ?:A novel?-?interaction and dual H-bond concerted control strategy to develop the first chiral phosphoric acids(CPAs)catalyzed direct intermolecular asymmetric C-H amination of N-aryl-2-naphthylamines with azodicarboxylates as amino sources for the construction of atroposelective naphthalene-1,2-diamines has been developed.The method features a broad range of substrates,high yields and ee values,providing a new strategy to chirality transfer via the modification of N-C atropisomers.Then,the reaction process is explored,and the roles of substituents on azodicarboxylates,phenyl and intramolecular hydrogen bond in stereo-control and stereo-stability are discussed.In summary,we have realized transition metal-catalyzed C-H amination directed by amide and chiral phosphoric acids(CPAs)catalyzed asymmetric C-H amination using azodicarboxylates as amino sources.