The Cross-Coupling Reaction Between N-H And P-H Via An Anodic Oxidation

Organic electrochemistry can be seen as a crossing field between organic chemistry and physical chemistry.Electrochemical organic synthesis is the use of electrical energy to accomplish the synthesis of organic compounds.It mainly focus on the electron gain and loss of organic compounds or redox media on the surface of the electrode,the interaction of anions,cations and molecules in solution,and the principles and characteristics of synthesis of new substances.The basic types of electrochemical organic reactions including oxidation and reduction of functional groups,addition,elimination,substitution,cracking and the use of redox media indirect synthesis reactions.With the concept of green chemistry protecting the environment and saving energy,chemists try to synthesize new substances via the methods of green chemistry.Electrochemical synthesis is a new method for sustainable development.Compared with the traditional chemical synthesis,electrolysis synthesis usually has the advantages of low toxicity of solvents,mild reaction conditions,high atomic economy,and simple reaction process.In addition,the electrochemical process utilizes the gain and loss of electrons to achieve redox reactions,and need not the addition of strong oxidation and reduction reagents,which is accorded with the requirement of green chemistry.Organic electrochemical synthesis technology also provides new ideas and methods for scientists.In this thesis,the cross-coupling reaction between N-H/P-H via an electrosynthesis was developed,and the synthesis of phosphinic amides was achieved under mild and metal-free conditions.The thesis altogether includes two parts.The first part summarizes the recent reviews of organic electrochemical synthesis and the construction of N-P bonds.The second part details the cross-coupling reaction between N-H/P-H via an anodic oxidation.First,on the basis of our laboratory's previous work on electrochemical synthesis and literature reports on the construction of N-P bonds,we developed a method for the synthesis of phosphinic amides under electrochemical conditions.Although the construction of N-P bonds via chemical methods has made good progress,these protocols usually suffered from some intrinsic disadvantages,including the stringent reaction conditions,low atom economy,the complex post-processing and unavailable substrates.These techniques limit their further application in organic synthsis.However,we succeeded in synthesizing phosphinic amides by electrochemical means,with the advantages of mild reaction conditions,wide range of substrates.high atom economy and environmental friendliness.Meanwhile,we proposed a plausible reaction mechanism through control experiments and achieved large gram-scale synthesis.In summary,we successfully devoleped the cross-coupling reaction between N-H/P-H via an anodic oxidation.Compared with the traditional chemical methods,electrochemical oxidation exhibits a series of attractive features:no transition metal,low toxicity of the solvent and high atom economy,which makes chemical synthesis greener in new direction.