Ir-systems modified with ferrocene-based homochiral diphosphonite ligands, prepared from functionalized SPINOL derivatives, promote benzamide-directed hydroarylative cross-couplings involving minimally activated alkenes. The processes are highly branched selective and enantioselective. Accordingly, tertiary benzylic stereocenters are generated under byproduct free conditions. This contrasts conventional cross-coupling approaches, which are less step and atom economical. Preliminary results show that the process extends to the formation of quaternary benzylic stereocenters.