Extremely facile ring inversion and rearrangement in fluorobicyclo[2.1.0]pentanes

cis-1,2,3,4,5,5-Hexafluorobicyclo[2.1.0]pentane and 1,2,4,5-tetrafluorobicyclo[2.1.0]pentane have been synthesized from hexafluorobenzene. The former hydrofluorocarbon, which exists entirely in the endo configuration, rearranges to cis-1,2,3,3,4,5-hexafluorocyclopentene below room temperature (Ea = 21.9 kcal/mol, log A = 13.4). The latter undergoes degenerate ring inversion with extraordinary ease (ΔG‡ = 6.8 ± 0.2 kcal/mol at −55 °C). Density functional calculations indicate that significant bonding between the bridgehead carbons is retained in the ring inversion transition state. Analogous calculations predict for hexafluorobicyclo[1.1.0]butane a considerably lower barrier for ring inversion and more 1,3-bonding in the transition state.

ΔG‡ = 6.8 ± 0.2 kcal/mol (−55 °C) Figure optionsDownload as PowerPoint slide