Electrochemical activation plays a key role in boosting substrate reactivity and directing unique cyclization patterns through the nature of intermediates. We report regioselective electrochemical selenocyclizations of ortho ‐alkynylbenzamides using diphenyl dichalcogenides in flow. The method enables exclusive 6‐ endo ‐dig cyclizations under mild and metal‐free conditions. Cyclic voltammetry and control experiments reveal that the oxidation potential of the substrates governs product selectivity. Mechanistic studies suggest that electrophilic selenium species activate alkynes via seleniranium intermediates. This sustainable approach offers a scalable route to selenium‐containing heterocycles with high selectivity and efficiency.
Gieman et al. (Wed,) studied this question.