Description:
<jats:p>An efficient and green synthetic method for the preparation of <jats:italic>N</jats:italic>,<jats:italic>N</jats:italic>‐disubstituted tetramethylpyrazinium radical cations was developed, which does not require any solvent or strong alkylating agents. The investigation by UV/Vis and electron paramagnetic resonance (EPR) spectroscopy proved the stability of the prepared radical cation. Moreover, it was shown for the first time that the prepared <jats:italic>N</jats:italic>,<jats:italic>N</jats:italic>‐disubstituted tetramethylpyrazine can act as a powerful metal‐free catalyst for the selective oxidative homocoupling of amines to the corresponding imines under solvent‐free conditions. Furthermore, oxygen or even air can be employed as an efficient oxidative reagent.</jats:p>