The buffered trifluoroethanolyses and acetolyses of exo-(2-D)- (6) and endo-(2-D)-5-norbornen-2-yl brosylates (7) yielded exo-5-norbornen-2-yl and 3-nortricyclyl derivatives. The deuterium distribution in these products was determined unambiguously by ²H-NMR. and MS. In contrast to previous reports, each hydrogen and, consequently, each deuterium atom could be identified. Product ratio and label distribution in the solvolysis of 6 make unnecessary the intervention of asymmetrical homoallylic cation intermediates. The results are most economically rationalized by invoking symmetrical 3-nortricyclyl ion-pair intermediates.