Study On The Synthesis Of Phosphonothioate (Phosphonoselenoate) In Water And Its Application In Allylation Reaction

This dissertation mainly studies the"one-pot"synthesis of phosphonothioates/phosphonoselenoates in water and copper catalyzed allylation of allylic phosphoro-thioates with aryl（benzyl）halides.The details are as follows:Firstly,a new method for the construction of P-S-C（sp³）and P-Se-C（sp³）bonds in water was developed.According to the"three components"and"one pot"strategy,high-efficiency coupling reaction of primary alkyl halides（or tosylates）,elemental sulfur（selenium）,and P（O）-H compounds under alkali-promoted was developed.This procedure affords valuable phosphonothioates（phosphonoselenoates）,including P-chiral compounds,with broad substrate scope and high efficiency.Moreover,this facile protocol also can be applied to gram-scale preparations.Secondly,the obtained phosphorothioate was applied to organic synthesis,and we have established an air-tolerable,copper-catalyzedα-selective allylation of allylic phos-phorothioate with aryl（benzyl）halide.And this reaction also provides excellentα-selectivity,the ratio ofα/?is up to 99:1.The combination of CuSCN/PPh₃ in the presence of LiCl and Mg in THF enabled the reaction to generate allylated products in high yields at ambient temperature.Moreover,it worked well for large-scale preparations under the present mild and easy-to-operate reaction conditions.