Zinc‐Promoted Synthesis of β‐(Thio)uredo‐Sulfides from Isothiocyanates and Tertiary Amines

Herein, we highlight the sequential Zn-promoted reactivity of isothiocyanates towards tertiary aliphatic amines with subsequent regioselective N-dealkylation, yielding respective thioureas. Under non-inert conditions Zn functions as a desulfurizing agent affording ZnS, while water acts as an oxygen source, facilitating the direct transformation of isothiocyanates into ureas. This strategy affords b-(thio)uredo-sulphides, important functionalities in synthetic and biological important functionalities. Through a comprehensive examination of the mechanism and substrate scope, we elucidate a non-radical pathway with Hofmann elimination as initial and desulfurization as final steps.