Reaction Sequences Involving the Mutual Interconversion of All 10 Tertiary Dimethyl-2-norbornyl Cations. A Comparison of Predicted Products and Rates with Experiment

Abstract

All 10 tertiary dimethyl-2-norbornyl cations have been prepared. There are sequences of individual steps which will in theory interconvert any given two of these cations, a total of 45 permutations. All of the possible sequences (within a defined limit on the allowable total number of steps) for performing these interconversions were determined using a digital computer. Each step used in the computer generated sequence had previously been assigned a trial activation free energy value and a comparison is made in this paper between the actual experimental rearrangement results (in terms of both the kinetics of disappearance for the cation and what product is in fact formed) and the predicted results.