Rhodium(III)‐Catalyzed Intramolecular Hydroarylation, Amidoarylation, and Heck‐type Reaction: Three Distinct Pathways Determined by an Amide Directing Group

The amide decides: Three different rhodium(III)-catalyzed reaction pathways of a wide variety of tethered alkenes can be accessed through changing the amide directing group. This provides an efficient route to a myriad of complex polycyclic products, many containing newly formed all-carbon quaternary centers. Amidoarylations can diastereoselectively deliver products with up to three contiguous stereocenters.