Perfluoroalkylation reactions via halogen-bonded electron donor-acceptor (EDA) complexes of amines and perfluoroalkyl halides under visible light

Amines are known to form halogen bonds with perfluoroalkyl halides, enabling the formation of electron donor–acceptor (EDA) complexes. In recent years, visible light-induced radical perfluoroalkylation reactions based on halogen-bonded EDA complexes have attracted increasing attention. This review provides a comprehensive overview of perfluoroalkylation reactions mediated by amines, categorized into two major sections: reactions employing amines as external catalysts and those in which the amines themselves serve as substrates and non-catalyze reactions. In the first part, we systematically summarize the types of amines used under optimal conditions and evaluated during conditional screening. By analyzing these reports, we highlighted the trends in amine selection for effective halogen bonding with perfluoroalkyl halides and identified the amines that have proven to be successful. The second part focuses on catalyst-free systems in which amines undergo perfluoroalkylation by acting as both halogen bond acceptor and reactive substrates. These examples were further classified based on the structural type of the anime. Finally, we discuss perspectives and future directions by considering unexplored and less-studied amines and their potential to form productive halogen-bonded EDA complexes with perfluoroalkyl halides. This structure-focused review aims to serve as a guide for designing new amine–perfluoroalkyl systems and for understanding the structure–reactivity relationships that govern visible-light-induced radical processes. • Various amines form halogen-bonded EDA complexes with perfluoroalkyl halides. • This review categorizes reactions according to the amine type. • Analyzing the trends in amine structure for efficient reaction progression • Non-catalytic reactions highlight substrate-controlled perfluoroalkylation pathways