Copper-Catalyzed Dynamic Kinetic Asymmetric C-P Cross-Coupling Reactions For The Synthesis Of P-Stereogenic Phosphine Oxides

P-chiral phosphines can act as important ligands in a variety of asymmetric catalysis.Such ligand catalysts play an excellent role in numerous highly enantioselective reactions.In addition,organophosphine compounds are used in a wide variety of industrial,agricultural and pharmaceutical applications.The enantioselective synthesis of organophosphine compounds is relatively difficult,and the use of asymmetric metal catalysis for the synthesis of organophosphines is an effective way,but most of them are currently catalysed using precious metals such as: palladium,ruthenium and rhodium,while we have used the inexpensive metal copper for catalysis,which can effectively reduce the cost of synthesis and obtain better yields and corresponding selectivity.Most of the currently available chiral organophosphine compounds have been synthesised using the induction of chiral cofactors,desymmetrization,kinetic splitting and dynamic kinetic splitting.While the first three methods have been more extensively developed,the use of dynamic kinetic splitting to synthesise organophosphines with high correspondence selectivity has been relatively less explored,mainly because of the need to find a substrate that can be racemic.Dynamic kinetic splitting can be effective in improving the economics of the atom and avoiding unnecessary losses.This paper focuses on the synthesis of chiral TPOs by dynamic kinetic disassembly of SPOs in the presence of cuprous iodide,chiral diamine ligands,and potassium carbonate.The method yields high yields and high enantioselectivity of TPOs with five,six and seven-membered rings.The method also allows for gram-scale scale-up reactions in which both yields and enantioselectivities are preserved,as well as the reduction of TPOs to trivalent cyclic organophosphine compounds.The reaction mechanism was also investigated and found that the substrate SPOs could be rapidly deprotonated under the combined action of copper,diamine ligands and bases,and the corresponding reaction mechanism was also proposed.