Transition‐Metal‐Free Dehydrogenative N–N Coupling of Secondary Amines with KI/KIO4

A transition‐metal‐free method for the dehydrogenative N–N coupling of secondary amines has been accomplished. This oxidative KI/KIO 4 protocol is mild and operationally simple. A diverse range of diphenylamines, carbazoles, and N ‐alkylanilines readily undergo N–N homo‐coupling effectively. Notably, the N–N cross‐coupling of two different arylamines is also demonstrated, which provides a straightforward approach to the complex N–N structures.