The linear-paired electrochemical synthesis of unsymmetrical sulfides by an anodic initiated mitsunobu-type activation of alcohols combined with the cathodic activation of disulfides under neutral conditions.

Herein, we describe the electrochemical transformation of primary and secondary alcohols with aromatic or aliphatic disulfides in an undivided cell under base-free conditions for the synthesis of sulfides. In the presence of PPh3 and n-Bu4NBr as supporting electrolyte a Mitsunobu like reaction is initiated at the anode while the disulfide is reduced at the cathode to generate the needed thiolate nucleophile. In a case study, a chiral secondary alcohol led to a retention in the presence and to an inversion of configuration in the absence of n-Bu4NBr.