AbstractDespite the prominence of C−N bond forming cross‐coupling reactions as a strategy to assemble molecular fragments, aminative coupling approaches, in which two fragments are assembled directly at the heteroatom, represents a rarely exploited retrosynthetic strategy. Herein, we report the design, synthesis, and implementation of an anomeric amide reagent capable of promoting highly regioselective aminative alkene‐arene and alkene‐alkene coupling reactions. This transformation follows a sequence of catalyst‐free chloroamination, N‐deprotection, and formal nitrene functionalization, all in one‐pot. Due to the simplicity of both the protocol and the building blocks required, high‐throughput experimentation (HTE) was employed, in combination with a full‐scale scope, to rapidly and efficiently explore a wide range of chemical space and determine the limits of reactivity. In addition, alternative reactivity modes from the functionalized intermediates delivered by this protocol demonstrate the divergent nature of this aminative coupling strategy.