A new type of ferrocene-based phosphine-tert-butylsulfinamide ligand has been synthesized and applied to the enantioselective formation of C–C and C–N bonds. The palladium complex derived from ligand 4a was an efficient catalyst in asymmetric allylic substitution of several substrate types. Enantioselectivites with the difficult substrate 3-acetoxycyclohexene of up to 91% ee are achieved.