The Use of Potassium/Sodium Nitrite as a Nitrosating Agent in the Electrooxidative N‐Nitrosation of Secondary Amines

Abstract We report herein on the electrochemical N ‐nitrosation of secondary amines using widely available sodium/potassium nitrite as a nitrosating agent. This approach not only eliminates the need for using a combination of sodium/potassium and a strong acid but also has good functional group tolerance. The reaction is compatible with the late‐stage modification of pharmaceutical compounds and could be conducted in gram scale with a high reaction efficiency. Preliminary mechanistic studies indicate that the N ‐nitrosation occurs via the anodic oxidation of KNO 2 into an NO 2 radical which is then transformed into an NO + cation.