Copper‐Catalyzed Dynamic Kinetic Asymmetric P−C Coupling of Secondary Phosphine Oxides and Aryl Iodides

Transition‐metal‐catalyzed enantioselective P−C cross‐coupling of secondary phosphine oxides (SPOs) is an attractive method for synthesizing P‐stereogenic phosphorus compounds, but the development of such a dynamic kinetic asymmetric process remains a considerable challenge. Here we report an unprecedented highly enantioselective dynamic kinetic intermolecular P−C coupling of SPOs and aryl iodides catalyzed by copper complexes ligated by a finely modified chiral 1,2‐diamine ligand. The reaction tolerates a wide range of SPOs and aryl iodides, affording P‐stereogenic tertiary phosphine oxides (TPOs) in high yields and with good enantioselectivity (average 89.2 % ee). The resulting enantioenriched TPOs were transformed into structurally diverse P‐chiral scaffolds, which are highly valuable as ligands and catalysts in asymmetric synthesis. An intermolecular dynamic kinetic asymmetric P−C coupling of secondary phosphine oxides and aryl iodides is catalyzed by copper complexes with a carefully tuned diamine ligand. The reaction features a broad substrate scope and affords the corresponding products with high yields and enantioselectivities. Versatile transformations of these products gave diverse P‐chiral scaffolds, which are valuable in asymmetric catalysis.