P‐Stereogenic Phosphines via Mn(I)‐Catalyzed Asymmetric Hydrophosphination of Vinyl Sulfones: A Case of Solvent‐Induced Stereoinversion

In this work, we report a novel approach for synthesizing P‐chiral phosphines through Mn(I)‐catalyzed enantioselective hydrophosphination of vinyl sulfones. A distinctive feature of this system is its solvent‐dependent stereoinversion, which enables the formation of products with opposite configurations using the same catalyst enantiomer. This phenomenon has been demonstrated across a range of vinyl sulfones and diarylphosphines, providing access to both configurations of P‐stereogenic phosphines with a single catalytic system.