Recent Innovations in Electrochemical C─H Functionalization of Heterocyclic Scaffolds: Mechanistic Insights Into Site‐Selective C─C and C─Heteroatom Coupling at Arene or Heteroarene Moieties

Abstract

This review surveys recent advances in the electrochemical synthesis of functionalized heterocycles via transition‐metal‐catalyzed C─H activation and functionalization, particularly focusing on reports published over the past 11 years (2015–2026) and with special emphasis on methodologies that avoid stoichiometric external oxidants or reductants. The covered transformations, including C─H phosphorylation, alkylation, alkynylation, arylation, and amination reactions, are organized according to the catalytic systems employed and the mechanistic pathways proposed. For each reaction class, the substrate scope, chemo‐ and regioselectivity, key mechanistic studies, and reported synthetic outcomes are summarized, and the potential advantages and limitations of the electrochemical approach are considered in relation to conventional protocols. Representative examples, from early pioneering studies to recent developments, illustrate where electrochemical conditions offer practical benefits in specific transformations and define the challenges that remain for broader synthetic application.