Recent Advances in Direct Deaminative Functionalization of Aromatic Amines

Deaminative functionalization has emerged as a powerful and versatile strategy in organic synthesis, enabling the construction of diverse aryl scaffolds from readily accessible aromatic amine precursors. While most existing approaches rely on preactivation of the amino group, the development of direct deaminative functionalization methods remains notably underexplored. This short review highlights recent advances in the direct deaminative functionalization of aromatic amines, with an emphasis on four distinct reactive in-situ generated intermediates, including pyridinium salts, isodiazenes, transient aryldiazonium species, and N-nitroamines. Complementary strategies, such as visible-light-induced deamination and η 6 -coordination catalysis, are also discussed. 1 Introduction 2 Deamination through Pyridinium Intermediates 3 Deamination via Isodiazene Intermediates 4 Deamination with Transient Aryldiazonium Intermediates 5 Deamination involving N-nitroamine Intermediates 6 Other Strategies 7 Conclusions and perspectives