Studies About Metal/Photo Catalyzed Carbon-Phosphorus Bond Formation

Organophosphine compounds have been widely used in medicinal chemistry and biochemistry due to their unique biological activities.Therefore,the development of effective and simple tactics to synthesize multifunctional organophosphine compounds have attracted much attention.This thesis separately summarizes the synthesis strategies of these two types about metal/photo-catalyzed C-P bond formation and describes the four highly functional organophosphine compounds synthesized by these two tactics in detail.This thesis includes the following five parts:1.The synthesis of organophosphine compounds was calssified and summarized in recent years.The content mainly focuses on the synthesis strategies of these two types about metal/photo-catalyzed C-P bond formation.2.The reaction of Rh（III）-catalyzed phosphine oxide migration was studied in detail.Inthisreaction,usingRh（OAc）₃·xH₂Oascatalyst,（2-azidostyryl）diphenylphosphine oxides as substrate,the 3-phosphinoylindoles were efficiently synthesized.Moreover,this intramolecular transformation offers a straightforward route to rebuild sp² C-P bond and construct the indole ring in one single step.3.Thereactionofsynthesisof2-phosphinoylindolesthrough phosphinoylation/cyclization of 1-isocyano-2-styrylbenzene at room temperature under irradiation without external oxidants was studied in detail.Preliminary mechanism investigations indicate that the benzyl radical as key oxidant to regenerate the ground-state photo-redox catalyst with completing the proposed catalytic cycle.4.The reaction of synthesis of multi-substitute cyclopropane compounds by using Ru（bpy）₃Cl₂·6H₂O as photo catalyst,diphenylphosphine oxide as substrate was studied in detail.This reaction was occurred at room temperature under irradiation with 5 W bule LEDs without external oxidants by using the olefin difunctionalization strategy.Preliminary mechanism investigations indicate that the reaction might involve a photo-redox process.5.The reaction of synthesis ofγ-oxo-phosphonates was studied in detail.In this reaction,using oxidized oxime phosphonates as phosphorus radical precursor,and fac-Ir（ppy）₃ as photo-catalyst,γ-oxo-phosphonates were efficiently synthesized by using semi-pinacol rearrangement process,and derivatized to obtainγ-hydroxyphosphoric acid.