A Unified Synthesis of Diazenes from Primary Amines Using a SuFEx/Electrochemistry Strategy.

Abstract

The electrochemical synthesis of 1,2-disubsituted diazenes via anodic oxidation of bench stable symmetrical and unsymmetrical sulfamides is reported. This work capitalizes on the streamlined preparation of diverse N,N'-disubstituted sulfamides using Sulfur(VI) Fluoride Exchange (SuFEx) click chemistry that were subsequently subjected to electrochemical oxidation to afford the desired diazenes. The electrochemical nature of the reaction conditions obviated the need for chlorinating reagents, which considerably improved the sustainability of the overall process. Noteworthy, in addition to the synthesis of alkyl diazenes, these milder conditions were shown to be competent for the formation of azobenzenes, albeit in lower yields. Mechanistic experiments were conducted to delineate the reaction pathway and to rationalize the formation of side products observed during the electro-oxidation of N,N'-diarylsulfamides.