Arylated amines are valuable motifs in organic synthesis due to their prevalence in natural products, pharmaceuticals and functional materials. 1 N-aryl amines are commonly prepared through transition-metal catalyzed cross-couplings 2 or by the increasingly popular C-H aminations. These methods are undeniably efficient and well established, however, their overall sustainability is compromised by the requirement of scarce metals and often expensive / time-consuming multi-step synthesis to attain more complex products with different N-aryl groups. Cyclic aliphatic amines constitute essential cornerstones in drug discovery, and methods for functionalization to modify their biological properties is of high value. Skeletal diversification trough ring opening by selective breakage of the strong C-N σ-bond 4 is a powerful strategy to change the overall shape of the molecule and achieve increased structural complexity. Such modifications have in the past been attained through reductive 6 or oxidative 7 pathways using transition metals or by von Braun type degradation via ammonium intermediates. However, there are limited examples of C-N bond cleavage that occur with simultaneous introduction of versatile functionalities at both the N-and C-terminal to afford complex value-added products, especially for unstrained cyclic amines. Diaryliodonium salts (Ar2IX) are acknowledged as excellent electrophilic arylating agents with desirable properties such as high reactivity, stability and synthetic accessibility. They have found extensive application in arylations of both carbon and heteroatom nucleophiles, 10 and are recognized as attractive multi-purpose reagents also in material chemistry. Their main drawback is the generation of stoichiometric ArI waste in the majority of their arylation pathways. To overcome this atomeconomy limitation, our group recently developed a sustainable strategy for incorporation of both aryl groups and the iodine of diaryliodonium salts 1 onto N-, O-and S-nucleophiles through a metal-free cascade reaction (Scheme 1A). Mechanistic studies suggested this atom-efficient diarylation to proceed through a novel pathway, with initial nucleophilic aromatic substitution (SNAr) followed by intramolecular arylation, as supported by isolation of SNAr intermediates A with O-and Snucleophiles. We envisioned that utilization of secondary amines in our diarylation strategy could lead to potent cascade reactions to yield a wide scope of functionalized diarylamines. Novel ortho- amino-functionalized diaryliodonium salts 3 could be synthesized through SNAr on 1, followed by a one-pot sequential arylation and ring-opening pathway via ammonium intermediates 4 (Scheme 1B). Upon C-N cleavage of 4 by external nucleophiles, 14 highly functionalized diarylamines 5, 6 would be obtained with excellent atom-and step economy. Moreover, diaryliodonium salts 3 with unprotected aliphatic amine substituents, could have interesting applications in organic synthesis and materials chemistry. They are, to the best of our knowledge, unknown in literature, which is likely due to the incompatibility of such functionalities with the oxidizing and acidic conditions required for the synthesis of diaryliodonium salts.