Electron-rich arenes such as anisole, dialkylbenzenes, and aniline and aryl ether derivs. underwent regioselective amination reactions with amines, amides, sulfonamides, and nitrogen heterocycles such as morpholine mediated by (hydroxy)(tosyloxy)aryliodanes and sulfonic acids in the presence of Cu(MeCN)4BF4 to yield para-substituted arylamines and arylated nitrogen heterocycles such as 4-(4-methoxyphenyl)morpholine in 20-82% yields. The reaction proceeded by generation of unsym. diaryl-λ3-iodanes in situ followed by copper-catalyzed amination. The structure of the unsym. diaryliodonium triflate 2,4,6-i-Pr3C6H2I+-3,4-Me2C6H3•OTf- was detd. by X-ray crystallog.