We herein present a method for preparation of previously synthetically inaccessible amino-functionalized diaryliodonium salts through an SNAr reaction with fluorinated diaryliodonium salts. After incorporation of a range of cyclic amines, these salts were efficiently utilized in a sequential arylation/ring opening pathway, allowing for skeletal diversification of this valued substrate class. The reaction takes place via an intramolecular arylation, forming an ammonium salt, which upon ring opening by external nucleophiles affords C-and N-functionalized diaryl amines. The reaction displays excellent functional group tolerance and transfer of aryl groups with varied electronic properties was demonstrated. The ring-opening allows for incorporation of common N-, O-, S-, C-, and halogen nucleophiles and derivatization of various natural products, giving a versatile set of amine products in a metal-free manner with high atom-and step-economy. The majority of the products contain a range of reactive sites/unprotected polar functionalities that increase their versatility and likeliness to attain medicinal applicability. 5b