Electrochemical Reduction of (1-bromo-2,2-dimethylpropyl)benzene in Dimethylformamide on Carbon Electrodes

Article abstract of DOI:10.1021/jo00388a028

Products from the electrochemical reduction of (1-bromo-2,2-dimethylpropyl)benzene (4a) on carbon electrodes in dimethylformamide containing lithium perchlorate were found to depend upon the electrolysis potential.At relatively positive potentials the products are derived primarily from the coupling of two benzylic radicals, wheres at more negative potentials the products are derived from the corresponding carbanions.This establishes for the first time the mechanism of bibenzyl formation in the electrochemical reduction of benzyl bromides at nonmetallic electrodes.It has also been found that the meso-dl ratios of the 1,2-di-tert-butyl-1,2-diphenylethane products are dependent upon electrolysis potential and that head-to-head coupling of 1-phenyl-2,2-dimethylpropyl radicals is sterically restricted.