Through the use of cyclic β-diketones as supporting ligands, the copper-catalyzed coupling of aryl iodides with aliphatic amines occurs at room temperature in as little as 1 h. These high reaction rates allow for the coupling of a wide range of aryl and heteroaryl iodides at room temperature. This method is highly tolerant of a number of reactive functional groups, including −Br and aromatic −NH2 as well as phenolic and aliphatic −OH. The high selectivity of the CuI−β-diketone catalyst for aliphatic amines represents a useful complement to the palladium-based methods.