Chiral Amide‐Enabled Iridium‐Catalyzed Asymmetric C–H Amidation for the Synthesis of P ‐Chiral Phosphorus Oxides

The development of chiral ligands that enable efficient asymmetric C–H functionalization remains a central challenge in asymmetric catalysis. Herein, we report a new class of chiral carboxamide ligands, in combination with an achiral [Ind*IrI 2 ] 2 catalyst, that promotes the enantioselective C–H activation of diarylphosphine oxides with p ‐toluenesulfonyl azide. The reaction proceeds under mild conditions to afford a range of P ‐stereogenic phosphine oxides featuring sulfonamide motifs in up to 75% yield and 94% ee. The synthetic utility of this method is demonstrated by the reduction of pentavalent phosphorus products to the corresponding P(III) compounds with complete stereochemical retention.