Cyclic voltammetry was employed in order to gain mechanistic insight into the electrochemical process. In accordance with the literature, 18d the combination of Mn(OTf) 2 and MgCl 2 produced a new quasi-reversible redox event at 0.8 V vs Fc/Fc + , which provided evidence for the generation of a Mn(III)X 2 Cl species from [Mn(II)X 2 Cl] -. Furthermore, a small increase in current was observed upon addition of 1-phenylcyclobutan-1-ol 1, which suggested that Mn(III)X 2 Cl is consumed by 1. When methyl ether cyclobutane 42 was employed as the substrate using the standard electrochemical reaction conditions, no γchlorinated ketone 2 was observed, with 82% starting material recovered (Scheme 3A). This indicated that the proposed MnCl 2 .4H 2 O (10 mol %), MgCl 2 (5 equiv.) LiClO 4 (0.1 M), MeCN/AcOH (7:1) i = 10 mA, j anode = 7.8 mA/cm 2 , Q = 3.73 F/mol undivided cell, 25 °C, 3 h, N 2 "standard" conditions