Electrochemically Driven Regioselective Radical Functionalization of Allenes: Scope and Mechanistic Insights

Despite their rich reactivity and unique cumulated π-system, allenes remain largely untapped platforms in electrochemical radical functionalizations. Herein, we report a regioselective electrochemical protocol that merges radical addition with anodic oxidative cyclization, enabling the construction of oxazoline and oxazolidine-2-imine frameworks under mild and sustainable conditions. Detailed mechanistic investigations along with DFT computational studies were carried out to probe the reaction pathway. These studies suggested selective radical addition at the central allenic carbon, forming an allyl radical intermediate that undergoes anodic oxidation and intramolecular nucleophilic cyclization, enabling efficient access to functionalized heterocyclic derivatives without external oxidants. This work unveils a new paradigm for electrochemically driven allene functionalization, expanding the scope of radical-mediated electroorganic synthesis toward biologically relevant moieties.