A DFT Study of the Camphene Hydrochloride Rearrangement

The rearrangement of camphene hydrochloride to isobornyl chloride is one of the best studied among the many early examples of Wagner-Meerwein rearrangement processes. However, many aspects of the reaction remain to be elucidated. A summary of early mechanistic studies is given. A proposal of new mechanistic possibilities is set forth and then tested by density functional theory (DFT) calculations. The uncertainties in configurations of camphene hydrochloride and isobornyl chloride are laid to rest by a comparison of computed and experimental carbon-13 and methyl proton chemical shifts.