Organic halides (R-X) are prevalent structural motifs in pharmaceutical molecules and key building blocks for the synthesis of fine chemicals. Although a number of routes are available in the literature for the synthesis of organic halides, these methods often require stoichiometric additives or oxidants, metal catalysts, leaving or directing groups, or toxic halogenating agents. In addition, the necessity of employing different, often tailor-made, catalytic systems for each type of substrate also limits the applicability of these methods. Herein, we report a clean halogenation by electrochemical oxidation with NaX/HX. A series of organic halides were prepared under metal catalyst-and exogenousoxidant-free reaction conditions. It is worth noting that this reaction has a broad substrate scope; various heteroarenes, arenes, alkenes, alkynes, and even aliphatic hydrocarbons could be applied. Most importantly, the reaction could also be performed on a 200-mmol scale with the same efficiency (86%, 50.9 g pure product).

Benzo­[4,5]­imidazo­[2,1-a]­isoquinolin-6­(5H)-one derivatives are prevalent in many synthetic intermediates, pharmaceuticals, and organic materials. Herein, we develop a Mn-catalyzed electrochemical radical cascade cyclization reaction that uses electricity as the primary energy input to promote the reaction, leading to a series of benzo­[4,5]­imidazo­[2,1-a]­isoquinolin-6­(5H)-one derivatives under exogenous-oxidant-free conditions. It is worth noting that this electrochemical method can not only realize the synthesis of benzo­[4,5]­imidazo­[2,1-a]­isoquinolin-6­(5H)-one derivatives but also provides a new strategy for generating alkyl radicals from alkylboronic acids.