Selective Radical N−H Activation: the Unprecedented Harnessing of Formamide with S8 for N−S−N Bonds Construction

A copper‐catalyzed novel, highly selective formamide (N−H) activation for the accessing broad range of formamide sulfides was developed. This strategy presented the first example on N−S−N bonds construction under mild conditions, featuring selective N‐radical based mechanism, as well as cheap, stable and environmentally friendly S8 as source of sulfur. In particular, this process was well defined by DFT calculation and a leading product was found to have significant anti‐fungal activity.