Transition Metal-Free Synthesis Of α-Aminophosphine Oxides Through C(sp3)-P Coupling Of 2-Azaallyls

Organophosphorus compounds(such as phosphine oxides)are widely used as catalysts and ligands in synthetic chemistry.α-Aminophosphine oxides have important biological and pharmacological properties,such as antitumor,anti-HIV,antibacterial and antituberculous activities,etc.They are also widely used in agrochemicals such as herbicides and plant virus killers.At present,the construction of α-aminophosphine oxide mainly used various transition-metal catalysts or ultrasonic radiation,electrochemical,and photocatalytic methods.However,these methods are usually limited by the harsh reaction conditions,addition of toxic metal catalysts,and stoichiometric oxidants.Based on the previous works of our group on imines,using diphenylphosphite chloride and imine as substrates,a new KHMDS mediated metal-free-catalyzed radical coupling reaction to α-aminophosphine oxides was developed in this thesis.This thesis is divided into three chapters.In the first chapter,the application and biological activity of organic phosphorus compounds and α-aminophosphine oxides,and the research progress in the synthesis of α-aminophosphine oxides were briefly reviewed.Based on this,the research topics of this thesis were proposed.In the second chapter,a new synthesis method of α-aminophosphine oxide was developed.Deprotonation of N-benzyl imines may generate super-electrondonor(SED)2-azaallyl anions that reduced chlorodiphenylphosphine oxides to phosphine oxide radicals.Single-electron transfer(SET)process transformed the 2-azaallyl anions into 2-azaallyl radicals,which may couple with phosphine oxide radicals to construct C-P bonds.By screening the reaction conditions such as base,solvent,temperature,time and concentration,a simple and efficient reaction condition was finally established.Then,the substrate scope of this reaction was studied.Different imine substrates and different chlorodiarylphosphine oxides were applied to synthesize 23 different types of α-aminophosphine oxides.The reaction mechanism was also studied.In the third chapter,the experimental partincluding synthetic experimental procedure and spectrum data of related compounds in the thesis was described.