Study On Synthesis Of Aryl Vinylphosphonate By Copper-Catalyzed Cross-Coupling Reaction Of Ketone Oximes With Alkenes

Aryl vinylphosphonates as an important kind of organophosphorus compounds and intermediates for synthesizing other organophosphorus molecules,were widely in many fields,such as used in organnic synthesis,photoelectric materials,retardant materials and medicinal chemistry.Aithough,more and more synthetic methods have been reported,these methods required the precious metals as catalyst and additional additives?oxidant and base?.Notably it was also difficult to synthesize some aryl vinylphosphonates with special structure.Thus,these disadvantages restricted their futher application.Therefor,developing a more simple,efficient,non-toxic and environment-friendly method for synthesizing aryl vinylphosphonates has become a hot spot fields for chemists in recent years.Based on this,we explored a new method for simple and mild synthesis of aryl vinylphosphonate.This thesis includes the next two parts:Chapter 1.Recent research progresses for the synthesis of aryl vinylphosphonate derivatives were reviewed systematically.Especially,the synthetic reactions of?-aryl vinylphosphonates under the catalysis of transition-metal-catalyzed?Pd,Ni,Cu,Ag and so on?were introduced in details,including cross-coupling reactions,hydrophosphorylation reactions and radical reactions.Moreover,the synthetic methods under metal-free conditions were also summarized.Chapter 2.A novel method for the synthesis of aryl vinylphosphonate derivatives was established.The synthetic strategy had two major advantages.First of all,this synthetic reaction was based on simple ketone O-benzoyloximes as phosphorus source.And then,a series of?E?-?-aryl vinylphosphonates derivatives were simply,efficiently and stereoselectively synthesized with the catalysis of Cu?OTf?₂.Subsequently,the mechanistic experiments demonstrated that the synthetic reaction might involve a radical process.