Electrochemical [4+2] Annulation‐Rearrangement‐Aromatization of Styrenes: Synthesis of Naphthalene Derivatives

We report the first electrochemical strategy to synthesize functionalized naphthalene derivatives through [4+2] annulation-rearrangement-aromatization from styrenes under mild conditions. The electrolysis does not require metals, oxidants and high valence substrates, indicating the atom and step-economy ideals. The dehydrodimer produced through [4+2] cycloaddition of 4-methoxy α-methyl styrene is isolated and proved to be the key intermediate for the following oxydehydrogenation to form carbon cation, which undergoes rearrangement-aromatization to afford the final products. This reaction represents a powerful access to construct multi-substituted naphthalene blocks in a single step.