Bifunctional Iminophosphorane Catalyzed Amide Enolization for Enantioselective Cyclohexadienone Desymmetrisation

We describe the organocatalytic enolization of 2‐arylacetamides, followed by an enantioselective intramolecular conjugate addition to tethered 2,5‐cyclohexadienones, yielding 3D fused N‐heterocycles. The transformation represents the first nucleophilic activation of carboxamides via α‐C–H deprotonation in a metal‐free, catalytic, and enantioselective reaction, and can be achieved by employing a bifunctional iminophosphorane (BIMP) superbase.