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.