Electrochemical Desulfurizative Amination of Heteroaromatic Thiols by Iodine Catalysis.

N‐Heterocyclic amines have been known as an important class of nitrogen‐containing molecules with a wide range of applications. Described here is a mild and efficient electrochemical desulfurizative amination of readily accessible heteroaromatic thiols without necessity of metal catalyst. The key to success for this reaction is the in‐situ generation of a hypervalent iodine reagent as an organocatalyst from iodoarene by anodic oxidation. This mild desulfurizative amination presents ample substrate scope and good functional group tolerance without the use of extra stoichiometric chemical oxidants. As only electrons serve as the oxidation reagents, this method offers a straightforward and sustainable manner towards versatile N‐heterocyclic amines, including late‐stage functionalization of pharmaceutically relevant molecules. [ABSTRACT FROM AUTHOR]