The addition of sodium hydride improved the yield of 2a significantly compared to the additive-free background reaction but was less efficient compared to the use of Bu4NBH4 as a reductant (Figure ). This difference suggested that the boron species generated upon borohydride electrooxidation may facilitate the deoxygenation via Lewis acid activation or boryl radical mediation, as reported under non-electrochemical conditions. However, when a selection of boron compounds were added to the reaction mixture (Figure ), none of the additives except the benchmark borohydride reagent improved the yield of 2a compared to the additive-free reaction, thus providing little support for this hypothesis. Recently, formation of borate esters intermediates between pinacolborane and alcohols were proposed in electrochemically driven deoxygenative borylation by Lin and co-workers. Such borate ester intermediates may be envisioned to form also in the present system from electrooxidatively formed borane and alcohols or in situ formed aldehydes. Indeed, trialkylborate esters were found to furnish the desired alkane products upon electroreduction as indicated by DFT as well as electrolysis of pre-formed 5a (Figure and ESI, Sections 7 and 12). However, no improvements in yield were observed when BH3•THF was used as additive in the reduction of 1a compared to the additive-free background reaction (Figure ) and mere trace amounts of product 2a were observed when aldehyde 3a was used as substrate (Figure ). Furthermore, trialkylborate ester 5b was not observed by B-NMR when a crude reaction mixture from electrolysis of 1b in d7-DMF was analyzed halfway into the reaction (see Section 7 in the ESI). Finally, the borohydride reagent and graphite anode could be replaced with a sacrificial Zn anode for the reduction of 1a to furnish 2a in excellent yield (Figure ), demonstrating that boron compounds are not necessary for a successful transformation. The combined experimental data, including the relatively forcing conditions required to synthesize benzylic trialkylborate esters (see Section 7 in ESI), in conjunction with the low barrier for C-O bond cleavage from the radical anion intermediate of the alcohol itself (Figure ), suggest that in situ formation and subsequent electroreduction of trialkylborate esters is unlikely to be the major mechanistic pathway in the present system. It can be noted that while C-O bond cleavage was facilitated in trialkylborate esters of -activated alcohols, aliphatic analogues displayed lower standard potentials compared to their corresponding alcohols and failed as hydrodeoxygenation substrates (see Sections 7 and 12-13 in the ESI). As such, alcohol derivatization to borate esters does not appear to be a generally applicable strategy to promote deoxygenative transformations in a reductive one-electron setting.