The Current State of the Art of Dearomatization Chemistry

When it comes to small organic molecules, aromatic compounds are considered to be one of the most abundant and versatile building blocks, currently produced on a hundred million metric ton scale each year. Moreover, due to their inherent resonance stabilization, arenes have been fascinating scientists for nearly two centuries and have also been serving as a never-ending inspiration for synthetic chemists. Arenes are in their own class of chemistry based on many unique reactivities that are associated only with this type of compounds. One such characteristic transformation is dearomatization – a type of reaction that can overcome aromatic stabilization and convert arenes into saturated, nonaromatic compounds. Historically, these transformations were limited to dearomative hydrogenations, dissolving metal reductions (Birch reaction), and oxidation of phenols; however, during the last couple of decades, the field has witnessed the exponential increase of novel dearomative strategies and fundamental advances in the field. Driven by the pressing need in medicinal and natural products chemistry to produce molecules with a dense array of functionality, increasing saturation (sp3 content), and different spiro- and polycyclic motifs, dearomatizations have become a platform to provide many solutions at the frontline of synthetic chemistry and molecular sciences. Incorporating advances and recent reactivity paradigms in catalysis, photochemistry, heterocyclic chemistry, electrochemistry, and biocatalysis, has led to a plethora of dearomative methods that have greatly expanded the scope and complexity of building blocks accessible from simple arenes. These include the enantioselective variants by employing strategies of asymmetric catalysis into the dearomatization processes. This issue offers a unique glimpse into the current state of the art of dearomatization chemistry. We thank the authors for their valuable contributions, which showcase how these transformations deliver unique molecular disconnections and products, provide one of the most rapid complexity-generating strategies in organic synthesis, and will continue to inspire us for years to come.