Searching for intermediates in Prins cyclisations: The 2-oxa-5-adamantyl carbocation

The 2-oxa-5-adamantyl carbocation 4 is shown to be a viable intermediate in several S1 substitution reactions. However, attempts to observe the formation of 4 from various precursors by NMR methods (which succeed for the 1-adamantyl cation 5) failed, suggesting that 4 does not survive on longer timescales. DFT calculations suggest that the retro-Prins process (β-cleavage, Grob fragmentation) to give enantiomeric (1R,5R)- and (1S,5S)-7-methylene-2-oxoniabicyclo[3.3.1]non-2-ene cations 22 is the only realistic unimolecular escape route for 4. With the 6-31G(d) basis set, B3LYP calculation predicts that 4 is only 11 kJ mol more stable than 22, and the barrier separating 4 and 22 is calculated to be only 15 kJ mol , so rapid equilibration of these species is likely on the laboratory time scale. The implications of this study for the mechanism of the Prins cyclisation are discussed. © 2010 The Royal Society of Chemistry.