LAUSR

An Ir-catalyzed regioselective hydroamination of allyl amines using aryl amines and catalyst-controlled regiodivergent hydroamination of allylic and homoallylic amines with aniline nucleophiles are reported. The 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 suggests 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 5- or 6-membered metalacyclic intermediate, depending on the catalyst employed.