Under the electrocatalytic conditions, methanol was found to add across a vinyl ether (5) in Markovnikov-selective fashion (Figure ). Inspired by recent reports on HAT-initiated alkene isomerization under chemical oxidation or electroreduction conditions as well as results from our own lab, we envisioned a tandem isomerization/hydromethoxylation reaction that leads to trapping at the more cation-stabilizing site (Figure ). The in situ hydrolysis of the resulting acetal would provide a cheap and chemoselective means for allyl deprotection, which is alternative to strong base-mediated or precious metal-catalyzed methods. Indeed, we were able to show efficient deallylation to reveal 1°, 2°, 3° alcohols, carboxylic acids, and anilines (Figure ). Conditions: substrate (0.30 mmol, 1 equiv.), 3a (5 mol%), TMDSO (2.0 equiv.), n-Bu4NBF4 (2.0 equiv.) in MeOH (3.0 mL), Pt mesh electrode, undivided cell, constant current i = 5 mA, 2.3 F/mol, 25 °C. b Yield was determined by 1 H NMR analysis of the crude reaction mixture.