Electrochemical Intramolecular Cyclization Strategies for the Synthesis of Pharmaceutically Relevant Fused N‑Heterocycles

Varga, Péter and Kovács, Ervin (2026) Electrochemical Intramolecular Cyclization Strategies for the Synthesis of Pharmaceutically Relevant Fused N‑Heterocycles. ACS ELECTROCHEMISTRY, 2 (4). pp. 845-873. ISSN 2997-0571

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Abstract

Nitrogen-containing fused aromatic heterocycles have a crucial role in the fields of pharmaceuticals, agrochemicals, and materials sciences. Electrochemical methods have increasingly emerged as powerful tools for the sustainable synthesis of these compounds. This review discusses recent progress in electrosynthetic strategies for fused systems that avoid the use of hazardous oxidants and extreme reaction conditions. There has been significant progress in the direct synthesis of various frameworks over the last few decades, specifically from 2015 to 2024. These advances are enabled by direct electrosynthetic approaches, mild redox mediators, and optimized electrolyte systems. These methodologies efficiently incorporate electron-rich and electron-deficient substrates, demonstrating broad tolerance to functional groups. Mechanistic investigations have revealed the pivotal role of radical and cationic intermediates, which are generated and controlled in situ. This facilitates regio- and chemoselective cyclization pathways. Ongoing research focuses on scalability, enhancing electrode stability, and expanding the diversity of accessible fused heterocyclic scaffolds. Innovations in this field highlight the potential of electrochemistry as a sustainable, versatile tool for synthesizing diverse nitrogen-containing fused aromatic heterocycles.

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