Difunctionalization Of Acetophenones And Synthesis Ofα-enaminones Via Electrochemical Oxidation

Organic electrolytic synthesis is called organic electrochemistry directly. This technology is an interdiscipline, which combines organic synthesis and electrochemical techniques. In this system we need not to add additional oxidants and reducing agents, gaining and losing electron directly to realize redox reaction, thus realizing the organic synthesis and getting the desired product. The basic types of electrochemical synthesis including the formation of carbon-carbon bonds and functional groups of addition, substitution, cracking, elimination, coupling, oxidation, reduction reactions and indirect electrosynthesis by using the media.With the development of science and technology, we now pay more and more attention to the protection of the environment. Therefore, chemists make efforts to realize green chemistry. Chemists also have been efforts to develop chemical reactions which are under mild reaction conditions, simple and environmentally friendly. Under organic electrochemical synthesis conditions, electron transferring is used to realize the redox reactions and electron is green and environmentally friendly. So organic electrochemical synthesis is more conform to the requirements of the development of the green chemistry and has the promising development prospect.This thesis mainly studies the formation of carbon-carbon and carbon-nitrogen in organic synthesis under electrochemical conditions, which are the realization of the difunctionalization of aryl ketones and the synthesis of a-enaminones via electrochemical oxidation respectively. The thesis altogether includes two parts, the first part summarizes the famous organic chemists’achievements about the functionalization of the sp3C-H of aryl ketones and the synthesis of a-enaminones; the second part details the difunctionalization of aryl ketones and the synthesis of a-enaminones via electrochemical oxidation.First, on the basis of previous work of our laboratory, we realized the difunctionalization of the sp3C-H of aryl ketones via electrochemical oxidation. Although the functionalization of the sp3C-H of aryl ketones has made good progress, but it mainly limited to the single functionalization of the sp3C-H of aryl ketones, the development of difunctionalization of aryl ketones is less. However, we successfully realized the difunctionalization of the sp3C-H of aryl ketones under electrochemical conditions. Besides, the reaction conditions are mild, the reaction can proceed well under atmospheric pressure, and the processing is simple, which are accorded with the requirement of green chemistry.Then, on the basis of the study, we developed the synthesis of a-enaminones under electrochemical and iodine catalytic conditions. Recently, the famous organic chemists have developed various ways to synthesize a-enaminones, but these methods have some limitations. Some’s substrates are just dicarbonyl compounds, some need to add the metal catalysts and oxidants, and the applicability of the substrates is not widely, which limits the development of the synthesis of a-enaminones. However, we realized the synthesis of a-enaminones via electrochemical oxidation. The method does not need to add any metal catalysts and oxidants and are friendly to environment. We successfully realize the green method to synthesize a-enaminones.In summary, we successfully developed the new methods to form carbon-carbon and carbon-nitrogen by organic electrochemical synthesis. The reaction system has a wide applicability of the substrates and has mild reaction conditions. Compared with the traditional chemical methods, this method is more green, the operation is simple, and this method provides a new direction for the green organic synthesis.