Activation of Elemental Sulfur by Electrogenerated Cyanomethyl Anion: Synthesis of Substituted 2‐Aminothiophenes by the Gewald Reaction

The activation of elemental sulfur (S₈) has been achieved by means of electrogenerated cyanomethyl anion [easily obtained by galvanostatic reduction from acetonitrile/tetraethylammonium hexafluorophosphate (MeCN‐Et₄NPF₆)]. The “activated” sulfur reacted with ylidenemalononitriles to give substituted 2‐aminothiophenes in very high yields. This variation of the Gewald reaction has been carried out using only catalytic amounts of electricity and supporting electrolyte. A proposed mechanism for the interaction between S₈ and cyanomethyl anion is described.