eCyanation: A Dual Strategy for Electrochemical Cyanation of Amines Using Potassium Thiocyanate

Electrophilic cyanation has long relied on highly toxic cyanogen halides, which limits practical use. Here we present eCyanation, an electrochemical approach that uses inexpensive, bench-stable potassium thiocyanate as the cyanide source. Under mild anodic conditions, electrophilic cyanating species are generated from thiocyanate, enabling N- and S-cyanation without handling cyanide salts or isolating cyanogen halides. For oxidation-sensitive substrates, we also provide a complementary two-step variant: bromine-mediated activation of thiocyanate generates a reactive cyanating solution, which is then combined with the nucleophile after electrolysis. Together, these two operational modes offer a practical entry point to electrophilic cyanation chemistry from thiocyanate.