Abstract: | A series of novel and easily accessed ferrocene‐based amino‐phosphine‐sulfonamide (f‐Amphamide) ligands have been developed and applied in Ir‐catalyzed asymmetric hydrogenation of aryl ketones, affording the corresponding chiral secondary alcohols with excellent results (up to >99% conversion, >99% ee and TON up to 200 000). DFT calculations suggest an activating model involving an alkali cation Li+. |