The Cubane Chronicles : Exploring Synthetic Routes Towards Cubanes

Kazi, Nahin and Coote, Susannah and McLaughlin, Mark (2026) The Cubane Chronicles : Exploring Synthetic Routes Towards Cubanes. PhD thesis, Lancaster University.

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Abstract

Cubane chemistry has expanded greatly since it was first synthesised in 1964 and is now recognised as a fascinating structure with unprecedented characteristics. Despite the significant advances that have been made in this field, synthetic routes towards cubane remain rudimentary and exist for few substitution patterns. Most available routes are not scalable and because of this, cubanes remain largely inaccessible and expensive – the result of which is a clear scarcity of investigations into their characteristics and applications by the scientific community. Thus, there is a clear gap in the literature for the scalable synthesis of cubane and its derivatives. The work entailed in this thesis is organised into three distinct parts: Chapter 2 discloses a new, scalable route towards 1,3-disubstituted cubanes that centres around a 1,3-carbonyl transposition via a Wharton rearrangement of an enone that serves as a precursor to 1,4-disubstituted cubanes, allowing the isolation of multigram quantities of 1,3-disubstituted cubanes for the first time. This chapter concludes with an exploration of decarboxylative transformations to provide functionalised, novel 1,3-disubstituted cubanes. Chapter 3 details an attempted synthesis of 1,2-disubstituted cubanes using azo dienophiles that relies on nitrogen extrusion to afford ring closure. In this route, ring closure was not observed due to a competitive ring-opening reaction to yield cyclooctatetraenes in the final step. Chapter 4 describes a preliminary investigation into a streamlined synthesis of 1,2-disubstituted cubanes that relies on biradical combination to elicit ring closure. Whilst preliminary results reveal a preference for the same ring-opening reaction observed in Chapter 2 during the ring closure step, intermediate functionalised basketenes and secocubanes were isolated in this work for the first time.