Isopropylidene quadricyclane 1 upon oxidation with catalytic amounts of the
electron transfer catalyst tris(p-tolyl)aminium hexafluoroantimonate (TTA(
.+) SbF6-) gives bicycloheptadiene 2 spontaneously and in quantitative yiel
ds. Epoxidation of the isopropylidene group drastically changes the reactiv
ity of the quadricyclane framework. Under the same reaction conditions (cat
alytic amounts of TTA(.+) SbF6-) norbornadiene 4 is formed spontaneously an
d quantitatively according to an NMR study. Theoretical calculations on the
model compounds quadricyclane 5a and isopropylidene quadricyclane 5b at th
e B3LYP/3-21G and MP2/3-21G level of density functional theory (DFT) and ab
initio theory reveal the mechanism of both reactions. In the parent quadri
cyclane system the concerted (but not synchronous) three-electron cycloreve
rsion is favored, and by hyperconjugation with the pi* orbital the isopropy
lidene derivative prefers a simultaneous cleavage of a "lateral" bond and a
cyclobutane bond to give the intermediate 9b. Starting from 9b there are t
wo pathways to the product bicycloheptadiene 12b. The pathway involving the
trimethylenemethane intermediate 11b turns out to be a dead end because th
e system has to overcome a very high activation barrier to give the bicyclo
heptadiene. Much more favorable and consistent with the reaction conditions
is a 1,2-shift, which has a barrier of only 1.7 kcal mol(-1), leading dire
ctly to the bicycloheptadiene radical cation 10b and subsequently upon redu
ction to the neutral product 12b. A number of known quadricyclane rearrange
ments can be explained by these mechanisms.