New Methods Of C(sp~2)-P Bonds Formations:Synthesis Of 2,3-bis(diarylphosphynyl)-1,3-butadienes And Phosphonyl Pyridines

Organophosphorus compounds have broad application in organic synthesis,medicinal chemistry and materials science.Therefore,the synthesis and application of organophosphorus compounds have attracted contirnuous attentions for synthetic chemists in recent decades.The nucleophilic substitution reaction between phosphonium halide and nucleophiles is the most commonly used method for constructing organophosphorus compounds.But the phosphonium chloride is air-and m oisture-sensitive and have pungent odor,which makes it hard to operate the reaction.This method also undergoes with harsh reaction conditions and poor compatibility of functional groups,thus limiting its application.In the past few years,transition-metal-catalyzed directed cross-coupling of P(O)H compounds has emerged as one of most promising strategies for construction of complex molecular frames in modern organic synthesis.2,3-bis(diarylphosphynyl)-1.3-butadienes bearing P-C-C-P backbones,which might farther transform to a new type of more useful diphosphine ligands by asymmetric hydrogenation of these motifs.This dissertation reported the first and efficient copper catalyzed directed twofold cross-coupling of unprotected propargylic diols with P(O)H compounds,providing a general,one-step approach to construct valuable P-C-C-P frameworks with operational simplicity and high step-and atom-economy under ligand-,and base-fr-ee conditions.Phosphonyl pyridines are a class of molecules with biological activity find widely applications in medicinal synthesis,ligand chemistry and photoelectric materials.Base-mediate cascade reaction between H-phosphine oxides and N-propargyl enaminones provide a new way to construct phosphonyl pyridine frameworks.The easily accessible compound as starting materi als without the need of transition metal are highly attractive for chemical synthesis from economic and environmental points of view since it could processed under mild conditions an d generated water as the sole byproduct.