Cp*CoIII‐Catalyzed C2‐Selective Addition of Indoles to Imines

Overriding innate reactivity: The utility of a CoIII catalyst to promote the C2-selective addition of indoles to imines was demonstrated. The CoIII catalyst completely changed the regioselectivity in comparison with simple Lewis acid catalyzed Friedel–Crafts C3-selective addition. High turnover number (TON) of the catalyst, up to 1.8×102 (with s/c=200; see scheme; s/c is the substrate/catalyst ratio), was achieved.