Metal

Catalysis

Reactivity (psychology)

Chromatography

Cascade

Alkyl

Nucleophilic aromatic substitution

Alternative medicine

Heteroatom

Combinatorial chemistry

Organic chemistry

Iodine

Nucleophile

Substituent

Hypervalent molecule

Medicine

Chemistry

Aryl

Nucleophilic substitution

Pathology

Chem

The arylation of heteroatom nucleophiles is a central strategy to reach diarylated compounds that are key building blocks in agrochemicals, materials, and pharmaceuticals. Nucleophilic aromatic substitution is a classical tool for such arylations, and recent developments in hypervalent iodine-mediated arylations allow a wider scope of products. Herein, we combine the benefits of these strategies to enable an efficient and transition-metal-free difunctionalization of N- and O-nucleophiles with two structurally different aryl groups and to provide di- and triarylamines and diaryl ethers in one single step (>100 examples). The core of this strategy is the unique reactivity discovered with specifically designed fluorinated diaryliodonium salts, which unveils novel reaction pathways in hypervalent iodine chemistry. The methodology is suitable for diarylation of aliphatic amines, anilines, ammonia, and even water. It tolerates a wide variety of functional and protecting groups, with the retained iodine substituent easily accessible for derivatization of the products.

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