Study On Three-component Reaction Of Aryne,Cyclic Sulfides And Diarylphosphine Oxides

Arynes,as electrophilic intermediates,can participate various type of transformations,including multicomponent coupling reaction,cycloaddition reaction,insertion reaction and etc.Recently,aryne chemistry has witnessed numerous progress,and draw great attention from the community.Organophorous compounds were widely present in the field of agrochemistry,coordination chemistry and chemical biology.Diarylphosphine oxides as an important class of P-containing reagents could participate radical reaction,ionic reaction and metal catalyzed coupling reaction to prepare various P=O containing building blocks.Nonetheless,literature search indicated that the use of diarylphosphine oxides in aryne based three-component reaction is very rare,which definitely require further studies.Herein,we systematically investigated a three-component reaction using Kobayashi aryne precursors,cyclic thioethers and diarylphosphine oxides.After carefully screening the reaction conditions,we found that in the presence of potassium fluoride/18-crown-6 as system and carbazole as the proton mediator,the ring-opening of cyclic sulfides with diarylphosphine oxides could be readily achieved in good yields.With optimal reaction conditions in hand,we studied the substrates scope of arynes,cyclic sulfides and diarylphosphine oxides.A wide array of structurally diverse phosphonates compounds were obtained in moderate to good yields.In fact,our protocol featured for mild condition and avoidance of transition metals,allowing the construction of C-P and C-S bonds in good efficiency.Moreover,product derivatization and scale-up synthesis also demonstrated the potential value of our method.Overall,our work offered an efficient alternative toward preparation of phosphonates compounds,and might expand the application of diarylphosphine oxides in aryne based three component coupling reactions.