Electrochemical Oxidative Dehydrogenative Thioacylation of N-Heterocycles with CS2 and Amines.

An electrochemical strategy is developed for valorizing sulfur-rich carbon disulfide (CS2) through thioacylation of nitrogen-containing heterocycles including carbazole and indole derivatives. This methodology employs CS2 and amines as readily available precursors to construct dithiocarbamate structures, creating an efficient electrochemical platform for synthesizing diverse dithiocarbamate-functionalized N-heterocycles. The metal- and oxidant-free process facilitates sequential N-C and N-S bond formation, delivering target products in high yields. Significantly, the transformation exhibits remarkable regioselectivity, favoring exclusive N-S bond formation at the indole nitrogen atom while suppressing competing C-S bond generation at the C3 position. Mechanistic investigations involving controlled experiments and radical trapping studies indicate that the reaction proceeds via a radical-mediated pathway.