The solvolytic behaviour of exo- and endo-bicyclo[3,2,1]octane-6-toluene-p-sulphonates

Abstract

The buffered acetolysis of exo-bicyclo[3,2,1]octane-6-toluene-p-sulphonate (12; R = OTs) has been found to give exo-2-bicyclo[3,2,1]octyl acetate, 40%(16; R = OAc), 2-bicyclo[2,2,2]octyl acetate, 44%(17; R = OAc), and exo-6-bicyclo[3,2,1]octyl acetate, 16%(12; R = OAc), whereas the corresponding endo-6-isomer (13; R = OTs) gave (16; R = OAc), 19%, (17; R = OAc), 21%, and (12; R = OAc), 60%. The significance of these results and those obtained from similar treatment of tricyclo[3,2,1,0^2,7]octane is discussed in terms of a hitherto unobserved 4,6-hydride shift in the bicyclo[3,2,1]octane skeleton.