New Strategy For Synthesis Of Phosphorous-Containing Compounds Via Photo/Metal Catalysis

Organophosphorus compounds are one of the most important multifunctional compounds.Because of their unique chemical properties and biological activities,organophosphorus compounds are widely used in chemistry,materials science,biology and agriculture.The development of simple and efficient strategies to synthesize organophosphorus compounds has always been a hot topic in organic synthetic chemistry.This thesis summarized the synthetic methods of organophosphorus compounds in recent years.Beside three new strategies for the synthesis of organophosphorus compounds that I have developed during my Ph.D.study.The thesis includes following five parts:1,The strategies for the synthesis of organophosphorus compounds by transition-metal-catalysis or photocatalysis that were developed in the past decades are classified and introduced.The functionalization of carbon-heteroatom bond,carbon-hydrogen bond,and carbon-carbon bond by transition metal was introduced separately,and it also covers the methods of transition metal and photocatalytic initiation of phosphine radicals to build carbon-phosphine bond.2,Visible-light-catalyzed phosphonylation-annulation reaction was studied.Base on the design of phosphine radical precursors,a series ofβ-Phosphonopyrrolidines andβ-Phosphonolactones compounds were synthesized through a photocatalytic strategy.3,The Heck-type reactions that were developed in recent years were organized in terms of olefine substrates.Hopeful,Heck-type reaction could provide some effectual methods in the synthesis of organophosphorus compounds.4,The aryl-substituted P-ligands with excellent diastereoselectivities were obtained though Heck-type reaction.This reaction combined the role of P（O）R₂ group to lead to high reactivity and high selectivity.A wide range of monoaryl-or diaryl-substituted P-ligands with excellent yields and diastereoselectivity were obtained.And this reaction provides a new strategy for the modification of phosphine ligands.The preliminary mechanistic studies demonstrated that it possibly underwent a cationic Heck reaction that was assisted by silver salt.5,P-involved heterocycle ring-closing-ring-opening rearrangement（HRR）promoted by Heck reaction.This reaction involved the participation of a nucleophilic solvent to realize the rearrangement of the arylphosphine group,which generated a series of phosphonate and phosphoric acid compounds with an indole skeleton.Compared with other reactions,this transformation provides an extremely simple and step-economic process for synthesis of a variety of indolyl-derivatives,and the products are the precursor of pro-chiral monophosphine ligands with important application value.