1,2‐Diiodobenzene is presented as an efficient catalyst precursor for the intermolecular amination of arenes under homogeneous conditions. N‐Troc‐ and N‐phthalimido‐substituted methoxyamines serve as suitable nitrogen sources providing the corresponding aniline derivatives in up to 99% yield and with up to 66:1 regioselectivity. Key for this successful CN coupling protocol is the strained μ‐oxo‐bridged