The Construction Of Hydrazine And Indolone Derivatives From Aromatic Amines

Hydrazine derivatives are significant intermediates for the synthesis of some natural products,drugs and organic materials,having been attract much attention in organic synthesis.In the past few decades,organometallic chemistry had progressed rapidly.A range of hydrazine derivatives were synthesized by employing transition metal catalysts.However,these strategies require the use of transition metal catalysts or oxidants.Recently,electrocatalytic organic synthesis,a new organic synthesis method,has the advantages of high efficiency,economy and pollution-free,which are consistent with the trend of sustainable development of green chemistry and popular with many researchers.Among them,the method based on electrocatalytic oxidative dehydrogenation coupling has developed rapidly and has become a research focus in organic synthetic chemistry.3,3'-Disubstituted-2-oxindole derivatives are the basic skeleton of many natural products and pharmaceuticals.It is a common nitrogen heterocyclic compound.3,3'-disubstituted-2-oxindoles have a wide range of applications in natural products and medicinal chemistry,such as antibacterial,anticancer,antiviral,and antiinflammatory,etc.Due to the diversity of physiological activities,they have received high attention from scientific workers.In recent years,most strategies have been reported for the synthesis of 3,3'-disubstituted-2-oxindole derivatives,in which most of them suffer from the use of toxic or precious transition metals,complex starting materials,multi-step reaction,and poor substrate scope.Thus,the development of a new method for the synthesis of 3,3'-disubstituted-2-indolones by using easily obtaining raw materials with environmentally friendly is also important to us.This paper mainly focuses on the construction of hydrazine and indolinone derivatives based on N-substituted aromatic amines.The electrocatalytic oxidation of N-substituted aromatic amines by dehydrogenation homo-and cross-coupling to form hydrazine derivatives and copper-catalyzed N-substituted aromatic Amines with?-carbonylalkyl bromides form 3,3'-disubstituted-2-indolinones have been achieved.This thesis consists of the following three parts:In chapter 1,recent development in the formation of hydrazine derivatives by N-substituted aromatic amines homocoupling and transition-metal catalyzed the formation of 3,3'-disubstituted-2-oxindole derivatives was first introduced.The homo-coupling reactions of N-substituted aromatic amines are described from two aspects: intramolecular homo-coupling and intermolecular coupling.The construction of oxindole was also described from those two aspects.In chapter 2,The dehydrogenative homo-and cross-coupling of electrocatalytic oxidation of N-substituted aromatic amines leading to hydrazine derivatives were discussed under electrocatalysis conditions.This reaction worked in a maneuverable undivided cell with constant current,which provided a new,powerful,and sustaniable strategy for the synthesis of various hydrazine derivatives.In chapter 3,a copper-catalyzed C-H [3+2] annulation of with N-substituted aromatic amines and ?-carbonyl alkyl bromides for the structure of3,3'-bisubstituted-2-oxindole derivatives was described.Oxindole derivatives were synthesized in one step from readily available feedstocks under copper catalyst system.A series of 3,3'-bisubstituted-2-oxindole derivatives were obtained based on the diversity of both reaction partners.