Our initial screenings demonstrated that pinacol borane (HBpin) was a promising coupling partner for the targeted desulfurative borylation of model compound benzyl phenyl sulfide (1a) (see ESI for details). Further evaluation of the reaction parameters (Table ) revealed that inexpensive graphite electrodes in an undivided cell with three equivalents of HBpin in THF with tetrabutylammonium borohydride (NBu4BH4) as supporting electrolyte furnished the boronic ester (2a) in quantitative yield at room temperature passing 10 mA cm -2 for 2 F under inert and anhydrous conditions (Table , entry 1). Similarly, other carbon-based electrodes boron doped diamond (BDD) and glassy carbon (GC) resulted in quantitative yield of 2a as well (Table , entries 2 and 3). For comparison, the use of metal electrodes (Sn cathode and Mg anode) with tetrabutylammonium bromide (NBu4Br) as supporting electrolyte were assessed. These conditions proved able to furnish the product 2a in quantitative yield (Table , entry 4), but these were determined less attractive due to the stoichiometric metal consumption for the anodic counter reaction. Switching from HBpin to bis(catecholato)diboron (B2Cat2) resulted in considerably lower yields of 2a subsequent to transesterification (Table , entry 5) (see ESI for details). The use of acetonitrile (MeCN) as solvent resulted in a lower yield of 2a even with increased amounts of HBpin (Table , entries 6 and 7). Non-anhydrous conditions failed to furnish 2a (Table , entry 8) and exchanging the N2 atmosphere for air resulted in a lower yield (Table , entry 9), highlighting the importance of dry and inert conditions. Furthermore, it was found that the amount of HBpin could be reduced to 1.5 equivalents (Table , entry 10) and these conditions were henceforth used. No reaction occurred in the absence of electricity (Table , entry 2), confirming that the transformation is indeed electrochemically triggered. Finally, the use benzyl mercaptan, the free thiol analogue of 1a, resulted in the target product 2a in poor yield, highlighting the role of the S-aryl group as an electroauxiliary in the benchmark substrate (entry 11), similar to its activating function in photochemical transformations. Table . Evaluation of reaction conditions Entry Deviation from above 2a (%) With optimized conditions at hand, the generality of the borylation protocol was assessed (Scheme 1). Gratifyingly, a variety of benzylic thioethers were successfully transformed into the corresponding pinacolboronic ester in good yields, including substrates with substituents such as reductively labile arylhalides (2b-d),