GRAPHICAL ABSTRACT
The electroreduction of a 1:1-mixture of 2-bromobenzyl 2,2-dimethylpropanedithioate and 2-bromo-5-methylbenzyl 2,2-dimethylbutanedithioate led to a mixture of 2-tert-butylbenzo[b]thiophene, 2-tert-amylbenzo[b]thiophene, 2-tert-butyl-5-methylbenzo[b]thiophene and 2-tert-amyl-5-methylbenzo[b]thiophene. The formation of the four different products instead of only the two expected compounds, 2-tert-butylbenzo[b]thiophene and 2-tert-amyl-5-methylbenzo[b]thiophene, which would result from a straightforward reductive cyclization of each dithioester, is indicative of a reaction pathway with cleavage of the intermediates and intermolecular recombination of the fragments.