Detection of an ylide intermediate in the electrochemically-induced Stevens rearrangement of an ammonium salt by in situ UV-vis spectroelectrochemistry

► Mechanistic insights of the electro-induced Stevens rearrangement are provided. ► The reduction of PhCOCH2N+(CH3)2CH2Ph is ascribed to a one-electron transfer process. ► An electrogenerated ammonium ylide has been detected by UV-spectroelectrochemistry.