To commence our studies, 1-phenylcyclobutan-1-ol 1 was selected as the model substrate (Table ). After extensive optimization, 17 it was found that an electrochemical system composed of MnCl 2 .4H 2 O (10 mol %) as catalyst, MgCl 2 (5 equiv.) as chloride source and LiClO 4 as supporting electrolyte in MeCN/AcOH (7:1, [1] = 0.05 M) using galvanostatic conditions (i = 10 mA, j anode = 7.8 mA/cm 2 , Q = 3.73 F/mol) and graphite electrodes at 25 °C for 3 h under N 2 , enabled the deconstructive chlorination of 1, giving γ-chlorinated ketone 2 in 82% NMR yield (entry 1). No conversion occurs in the absence of electricity or the manganese catalyst (entries 2 and 3). Employing a constant cell potential (E cell = 2.4 V) or variation of the current (i = 12.5 mA or 7.5 mA) lowered the NMR yield of 2 (entries 4-6). Employing TBAPF 6 as electrolyte (entry 7) or substituting the graphite cathode for Pt foil or Ni plate (entries 8 and 9) each had a negligible impact on conversion. However, upon evaluating alternative Mn(II) salts (entries 10 and 11), it was found that