Rhodium-/Iridium-Catalyzed Hydroamination for the Synthesis of 1,2‑, 1,3‑, or 1,4-Diamines

The Ir-catalyzed regioselective hydroamination of allyl amines as well as the catalyst-controlled regiodivergent hydroamination of homoallylic amines with aniline nucleophiles is reported. These directed hydroamination reactions afford a variety of 1,2-, 1,3-, and 1,4-diamines in good to excellent yields and high regio- and chemoselectivities. Mechanistic investigations suggest that the reactions are proceeding through an oxidative addition into the ArHN–H bond and that the observed regioselectivity is due to the selective formation of a five- or six-membered metallacyclic intermediate depending on the catalyst employed.