Exploring Cuneanes as Benzene Isosteres and Energetic Materials: Scope and Mechanistic Investigations into Regioselective Rear-rangements from Cubanes

24 January 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Cuneane is a strained hydrocarbon accessible via metal-catalyzed isomerization of cubane. The carbon atoms of cuneane define a polyhedron of the C2v point group with six faces- two triangular, two quadrilateral, and two pentagonal. The rigidity, strain, and unique exit vectors of the cuneane skeleton make it a potential scaffold of interest for the synthesis of functional small molecules and materials. However, the limited previous synthetic efforts towards cuneanes have focused on mono-substituted or redundantly substituted systems such as permethylated, perfluorinated, and bis(hydroxymethylated) cu-neanes. Such compounds, particularly rotationally symmetric redundantly substituted cuneanes, have limited potential as building blocks for the synthesis of complex molecules. Reliable, predictable, and selective syntheses of poly-substituted cuneanes bearing more complex substitution patterns would facilitate the study of this ring system in myriad applications. Herein, we report the regioselective, AgI-catalyzed isomerization of asymmetrically 1,4-disubstituted cubanes to cuneanes. In-depth DFT calculations provide a charge-controlled regioselectivity model and direct dynamics simulations indicate that the non-classical carbocation is short-lived and dynamic effects augment the charge model.


skeletal rearrangement
benzene bioisostere
reaction mechanism


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