An Electrocatalytic Newman-Kwart-type Rearrangement.

An electrochemical approach toward rearrangement of O-aryl thiocarbamates to the corresponding S-aryl thiocarbamates is presented. The protocol requires only catalytic amounts of electric charge and allows for operation at room temperature. The electrolysis can be carried out with the simplest equipment, i.e., under galvanostatic conditions in an undivided cell. Furthermore, it is demonstrated that when the electrolysis is performed in a microflow reactor, almost quantitative yields can be achieved without using supporting electrolyte.