Occurrence, synthesis and applications of natural and designed [3.3.3]propellanes

The synthetically challenging [3.3.3]propellane core has caught a lot of attention over the last 50 years. This comprehensive review details all synthetic strategies reported in the period 1978–2019 to facilitate the synthesis of carbocyclic [3.3.3]propellanes. The described strategies span from acid-catalyzed rearrangements and photo-mediated cycloadditions of ketones, heteropropellanes and dispiroundecanes to thermal rearrangements of acetylenes and alkenes. Other approaches, such as radical reactions with halogenated alkenes, domino cyclizations, the smart use of epoxide-carbonyl rearrangements and intramolecular palladium-catalyzed ring contractions are discussed as well. A special section is dedicated to triptindanes, a subclass of [3.3.3]propellanes which are of interest to material sciences.