Metal‐Free Amination of Imidazoheteroarenes Employing p ‑Quinone Diimides ( p ‑QDIs)

In this study, we present a catalyst‐free efficient, and sustainable synthetic strategy using p ‐quinone diimides ( p ‐QDIs) as versatile electrophilic reagent for the amination of substituted imidazo[1,2‐ a ]pyridines and benzoimidazo[2,1‐ b ]thiazoles. This method enables amination of imidazoheteroarenes under mild, metal free, and environmentally friendly reaction conditions, thereby avoiding the use of, external oxidants, or other hazardous reagents. The reaction operates through an electrophilic 1,6‐addition mechanism, in which p ‐QDIs, act as strong electron deficient species that promote direct C‐N bond formation at the heteroaromatic framework. The developed method exhibits a broad substrate scope and functional group tolerance, providing amination products in good to excellent yields across diverse structural frameworks. Moreover, a one‐pot synthetic protocol has been successfully established, further improving the operational simplicity, atom economy, and overall practicality of the process. The catalyst‐free transformation represents a sustainable and scalable approach for the selective functionalization of imidazoheteroarenes, offering great potential in pharmaceutical and heterocyclic chemistry.