Benzamide‐Directed Hydroarylative Cross‐Couplings Using Minimally Activated Alkenes: Enantioselective Synthesis of Tertiary and Quaternary Stereocenters

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.