Magnesium-Catalyzed Hydrophosphinylation Of Alkenes With Diphenylphosphine Oxides

Due to the wide practical applications of organophosphorus compounds containing a phosphoryl group in medicinal chemistry,agrochemistry,materials chemistry and organometallic catalysis,an efficient and atom-economical construction of P^v（O）-C building blocks has engendered significant research interest.Among which,direct addition of P^v（O）-H to alkene represents a simple and atom-economical approach to P^v（O）-C bond formation reactions,which are generally accomplished by the generation of phosphinoyl radical or transition-metal catalysis.However,main group metal-catalyzed hydrophosphinylation of alkene is scarcely reported.Thus,it is of certain significance to develop the alkene hydrophosphinylation with main group metal catalysis,which is cheap and easily available compared with transition metals.In this paper,the main group metal magnesium complex LMgBu（L=HC（CMeNAr）₂,Ar=2,6-ⁱPr₂C₆H₃）was synthesized and applied as catalyst for the reaction between alkenes and diarylphosphine oxides.This hydrophosphinylation reaction is amenable to structurally diverse alkenes and can successfully afford a series of organophosphorus compounds,which are fully characterized.Mechanistic studies revealed that LMgOPPh₂ generated form the reaction of LMgBu and Ph₂P（O）-H is an active catalytic species.Notably,this transformation represents perfect atom economy and high regioselectivity.This paper has the following work:（1）Magnesium-catalyzed hydrophosphinylation of mono/disubstituted alkenes and α,β-unsaturated alkenes with diphenylphosphine oxides.（2）Magnesium-Catalyzed hydrophosphinylation of styrene with diarylphosphine oxides.（3）Hydrophosphinylation of alkenes containing cholesterol and oxaprozin skeleton was carried out respectively.（4）Mechanistic studies revealed that LMgOPPh₂ is the active catalytic species.（5）Synthesis of substrate alkenes and diarylphosphine oxides.