Metal‐Free Electrochemical Reduction of Disulfides in an Undivided Cell under Mass Transfer Control

Electroorganic synthesis is generally considered to be a green alternative to conventional redox reactions. Electrochemical reductions, however, are less advantageous in terms of sustainability, as sacrificial metal anodes are often employed. Divided cell operation avoids contact of the reduction products with the anode and allows for convenient solvent oxidation, enabling metal free greener electrochemical reductions. However, the ion exchange membranes required for divided cell operation on a commercial scale are not amenable to organic solvents, which hinders their applicability. Herein, we demonstrate that electrochemical reduction of oxidatively sensitive compounds can be carried out in an undivided cell without sacrificial metal anodes by controlling the mass transport to a small surface area electrode. The concept is showcased by an electrochemical method for the reductive cleavage of aryl disulfides. Fine tuning of the electrode surface area and current density has enabled the preparation of a wide variety of thiols without formation of any oxidation side products. This strategy is anticipated to encourage further research on greener, metal free electrochemical reductions. Electrochemical reductive cleavage of disulfides has been accomplished without the need for sacrificial metal anodes or a divided cell. Excellent conversion and selectivity toward the corresponding thiol can be achieved by tuning the current density at the electrodes. Very high current density at the anode creates a mass transfer barrier that impedes re‐oxidation of the thiol generated at the cathode.