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Updated: Oct 10, 2025

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Ambimodal Pericyclic Rearrangements of Dialkenyl-Bullvalenes Give Tetrahydro-1,8-ethenoheptalenes
Harshal D Patel1, Sebastian Gaggl1, Lukáš F Pašteka2
1Department of Chemistry, The University of Adelaide, Adelaide, SA 5005, Australia.
Abstract:
The fluxional structure of bullvalene is expanded by the discovery of a [5,5]-sigmatropic rearrangement of dialkenyl substituted derivatives. This gives rise to tetrahydro-1,8-ethenoheptalenes (THEH), representing the first examples of this tricyclic scaffold. Variation of the substitution pattern alters the product distribution, including one thermodynamically balanced between THEH and bullvalene isomers. DFT calculations are used to explore the thermodynamic landscape and reaction mechanism revealing a pretransition state bifurcation leading to a concerted ambimodal rearrangement pathway.
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