Diarylation of N- and O-nucleophiles through a metal-free cascade reaction

•Novel SNAr reactivity discovered with ortho-fluorinated diaryliodonium salts•Efficient diarylation of water, ammonia, primary amines, and anilines•Convenient simple route to triarylamines three different aryl groups•The products are easily derivatized through the retained iodide substituent Diaryl ethers, diarylamines, key structural motives in natural products, pharmaceuticals, material chemistry. Nevertheless, production highly functionalized derivatives these substance classes often requires time-consuming expensive multi-step syntheses, as methods for simultaneous introduction two structurally groups lacking. In this study, we present an atom-efficient metal-free difunctionalization N- O-nucleophiles one step. We anticipate methodology be a competitive sustainable alternative established arylation due broad scope, high functional group tolerance, excellent yields. The reaction setup avoidance toxic, sensitive, or reagents/catalysts grant utility outside advanced organic chemistry laboratories. Importantly, novel mechanism is expected enable new opportunities hypervalent heteroatom nucleophiles central strategy reach diarylated compounds that building blocks agrochemicals, materials, pharmaceuticals. Nucleophilic aromatic substitution classical tool such arylations, recent developments iodine-mediated arylations allow wider scope products. Herein, combine benefits strategies efficient transition-metal-free provide di- diaryl ethers single step (>100 examples). core unique specifically designed fluorinated salts, which unveils pathways iodine suitable aliphatic anilines, even water. It tolerates wide variety protecting groups, accessible derivatization O-arylated motifs pharmaceuticals.1Ruiz-Castillo P. Buchwald S.L. Applications palladium-catalyzed C-N cross-coupling reactions.Chem. 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