1-Adamantyl cation degenerate rearrangement

Olah and coworkers NMR study of the 8,9-dehydro-2-adamantyl cation, obtained from the corresponding alcohol in superacidic medium, showed the equivalence of C2, C8 and C9 carbons ((5 C 157.0) in agreement with the conclusions of solvolytic studies Even at -120 °C the structure of the cation could not be frozen out to a static cation, showing the extremely fast equilibration of the threefold degenerate cyclopropylcarbinyl cation 74. An identical NMR spectrum was obtained from the ionization of the 2,5-dehydro-4-protoadamantanol, which prompted the suggestion of the intermediacy of the 2,5-dehydro-4-protoadamantyl cation 75. The ion rearranges to an ally lie cation 76 at -78 (equation 45). 

With the aim of studying a geometrically well-defined cyclopropylcarbinyl cation Baldwin and Foglesong (1968a) prepared the 8,9-dehydro-2-adamantyl 3,5-dinitrobenzoates [125 X = H, D or T]. The solvolysis of [125] in 60% aqueous acetone proceeded with considerable rate enhancement in comparison with 2-adamantyl tosylate. Scrambling of the label to the 8 and 9 positions in the solvolysis of [125 X = D] and [125 X = T] revealed a degenerate rearrangement (90) of the intermediate 8,9-dehydro-2-adamantyl cation [126]. 

Since the symmetry of the spectrum was incompatible with either a static bridged 2-adamantyl cation (157) or a static protoadamantyl cation (158), two mechanisms were postulated involving sets of the cations from 157 or from 158 undergoing rapid degenerate rearrangements at -47°C [Eqs. (5.23) and (5.24)] ... 

DEGENERATE CARBOCATION REARRANGEMENTS 8,9-dehydro-2-adamantyl and related cations... 

---