Pd-catalyzed asymmetric P–C cross-coupling to access ortho-NH2 or -OH aryl P-chiral phosphine oxides

<h2>Summary</h2> A direct enantioselective P–C cross-coupling of secondary phosphine oxides with unprotected <i>ortho</i>-NH₂ or -OH aryl iodides is facilitated by a Pd-PHOX ligand catalyst. Here, we report a facile and straightforward approach for synthesizing free <i>ortho</i>-amino- or -hydroxy-substituted P-chiral phosphine oxides, achieving good yields and high ee values. Moreover, the chiral phosphine products derived from this process are successfully utilized to construct thiourea catalysts and potential bidentate Lewis base catalysts, which show promise in reductive aldol reactions. Additionally, density functional theory (DFT) calculations are performed to elucidate the origin of enantioselectivity and the generality of this method.