Electrochemical Chemo‐ and Regioselective Heterofunctionalization of Tropones via C( <i>sp</i> ² )H Derivatization

A general electrochemical synthetic procedure for the site‐selective heterofunctionalization of activated tropones is documented. Detailed voltametric analysis and quantum chemistry calculations enabled the development of a predictive model for the process efficiency, accounting for both reactivity and regioselectivity. Mono‐ and poly‐halogenation, nitration, sulfonation, and thiocyanation protocols are successfully executed starting from inexpensive sodium salts under oxidative electrolytic conditions (35 examples, isolated yields up to 95%, faradaic efficiencies up to 95%). The implementation of an iterative electrochemical/metal‐catalyzed cross‐coupling synthetic strategy, along with the adaptation of the protocol for the preparation of biologically relevant tropolone derivatives, underscores the generality and robustness of the methodology.