While -methoxylations of electron-deficient -amino acid carbamates have been reported by the Shono group, the scope has been limited to sterically less demanding methyl carbamates. To render more versatile protecting groups, e.g. benzyl and tert-butyl carbamates, accessible, we started to explore conditions tolerant thereof. In addition, we aimed at developing a mild elimination protocol to afford dhAAs. We initiated our investigation of the anodic oxidation with Boc-Ala-OMe (1a) as the model system for exploring suitable conditions for the Shono-type oxidation. Reaction optimization revealed the -methoxylation to proceeded virtually quantitative using NaCl (60 mol%) as a mediator, LiClO4 as electrolyte and MeOH (0.3 mol/L) as the solvent (Table , entry 1, see Supporting Information for full table). The reaction did not proceed in the absence of NaCl (entry 2) and the faradaic efficiency dropped significantly at lower substrate concentrations (entries 3-4). Without LiClO4, the product 2a was obtained in a significantly lower yield of 83% (entry 5). a Reaction conditions: 1a (1.0 eq., 0.3 M), NaCl (0.6 eq.), LiClO4 (0.1 M), 8.2 mm graphite electrodes, J = 5 mA/cm 2 , 4 F/mol, rt, air atmosphere.