Iron‐Sulfate‐Catalyzed Direct Dehydrogenative Coupling Cyanation of Secondary Phenylamines

A direct dehydrogenative coupling cyanation of secondary phenylamines was developed under iron sulfate catalysis by utilizing trimethylsilyl cyanide as a cyano source and tert ‐butyl hydroperoxide as oxidant. A variety of α‐aminonitriles, which commonly serve as versatile synthetically important intermediates, were synthesized in isolated yields of up to 90 %. Based on control experiments, the cyanation mechanism might involve a single‐electron transfer and a subsequent formation of an iminium ion.