Cyclic voltammograms for the reduction of ethyl 2-bromo-3-(3',4'-dimethoxyphenyl)-3-(propargyloxy) propanoate (1) at a silver cathode in dimethylformamide (DMF) containing 0.10 M tetraethylammonium tetrafluoroborate (TEABF4) exhibit several cathodic peaks, the first of which is attributed to reductive cleavage of the carbon-bromine bond. Controlled-potential (bulk) electrolyses of 1 at silver gauze electrodes in DMF-0.10 M TEABF4 give rise to four products: cis-and trans-isomers of ethyl 3-(3',4'dimethoxyphenyl)- prop-2-enoate (4), ethyl 3-(3',4'-dimethoxyphenyl) propiolate (7), and ethyl 3-(3',4' -dimethoxyphenyl)-3-(prop2- yn-1-yloxy) propanoate (8). These products have been identified with the aid of mass spectrometry and nuclear magnetic resonance spectroscopy. We propose that reduction of 1 involves two-electron cleavage of the carbon-bromine bond to form a carbanion. Then the latter species eliminates -OCH2C= CH to afford 4. In addition, -OCH2C= CH can deprotonate 1 to yield (Z)-ethyl 2-bromo-3( 3',4' -dimethoxyphenyl) acrylate (5), which is further deprotonated by -OCH2C= CH to give 7. Alternatively, the carbanion resulting from the original two-electron reduction of 1 can gain a proton from the medium to form 8. (C) The Author(s) 2014. Published by ECS. All rights reserved.