Nickel-Catalyzed Synthesis Of P-Stereogenic Compounds

Chiral phosphorus compounds are a class of chiral molecules which are widely used in various areas.Chiral trivalent phosphorus is one of the most commonly used organic small-molecular catalysts,and it is often used as a chiral ligand for transition metal catalysis.P-stereogenic compounds are chiral compounds with chiral center on phosphorus atom.They play irreplaceable roles in asymmetric catalysis,biochemistry and pharmaceutical chemistry.However,its rapid development and application are greatly limited by the lack of efficient synthesis methods.In the first chapter of this paper,the importance of P-stereogenic compounds and their synthesis research progress will be introduced in detail.We first briefly introduce the traditional methods of synthesis of P-stereogenic compounds,such as chemical resolution,asymmetric deporotonation and chiral auxiliary induction.Then we focus on the summary and introduction of catalytic asymmetric synthesis strategies,especially transition metal catalytic asymmetric synthesis strategies,including catalytic desymmetry,catalytic asymmetric conversion strategies based on secondary phosphine oxide,secondary phosphine and H-phosphinates.In the second chapter,we will introduce our development of nickel-catalyzed asymmetric allylation reaction to construct P-stereogenic chiral phosphine esters.We used Ni（COD）₂/QuinoxP^* catalytic system to realize the asymmetric cross coupling of branched allyl acetates and H-phosphinates.The reaction was carried out though the dynamic kinetic asymmetric transformation of H-phosphinates,so we used excessive H-phosphinates to ensure the selectivity and reactivity of the reaction.In the third Chapter,we will introduce our recently completed nickel-catalyzed asymmetric P-arylation reaction to synthesize chiral diarylphosphinic esters using commercial aryl iodide as the arylation reagent,which not only realizes the asymmetric arylation of H-phosphinates,but also finds that our method is applicable to the asymmetric arylation of secondary phosphine oxides.In this method,we use a cheaper and easily available bivalent nickel salt as the catalyst precursor,which makes the reaction easier to operate and more economical.In conclusion,we first summarized the full text and found the shortcomings of our work and the areas for improvement.Then,we analyzed the existing problems in the synthesis of P-stereogenic,and proposed possible solutions.We predict the main direction of the synthesis of chiral compounds with phosphine centers in the future,including the discovery and development of new phosphorus reagents and the development of dynamic kinetic asymmetric transformation methods.Finally,we hope that more researchers will participate in the synthesis of chiral compounds with phosphorus centers,especially the catalytic asymmetric transformation of phosphinic acid derivatives.