Small rigid hydrocarbon molecules such as cubane or bicyclo(1.1.1)pentane (BCP) are used as bioisosteres in medicinal and materials chemistry and offer potential as rigid (linear) and isolating linker units in electron transfer compounds, as molecular tectons in supramolecular chemistry and as molecular scaffolds with defined geometry. Despite being known for a long time, generally applicable synthetic methods for their functionalization and use are only slowly emerging.<br/>Our recent work in this area entailed first developing methods for the substitution of cubane with heteroatoms and was followed by adopting redox-active esters for the synthesis of 1,4-disubstituted aryl and heteroaryl derivatives, including porphyrins. Additionally, bisalkynylcubanes could be used in Sonogashira-type couplings with bromoporphyrins for the construction of complex porphyrin arrays in excellent yields. In connection with their use as bioisosteres crystal engineering studies and an analysis of solid-state interactions in cubane derivatives were performed and illustrate their ability to participate in unique bonding patterns.<br/>Current studies target complex amide linked porphyrin donor-acceptor dyads with cubane and/or BCP linkers and the development of functionalization methods for propellane and BCP. The latter aims to deliver simple but general BCP derivatives for use in synthetic, supramolecular and materials chemistry.

Cubane and bicyclo(1.1.1)pentane: Rigid hydrocarbon linkers for flexible uses

ACS Fall 2021

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