An alcoholate function intramolecularly induces heterolysis of a sulfonate ester group in an apolar solvent via orbital interactions through three intervening C-C single bonds (TBI). It is shown that the reactivity of rigid trans-perhydronaphthalene-1,4-diol monosulfonate esters (1-6) upon treatment with sodium tert-amylate in refluxing benzene is only affected by the relative position of the hydroxyl function to the sulfonate ester group and not by the orientation of the hydroxyl group. The two chief pathways by which these compounds react are rearrangement (1, 3, and 4) and homofragmentation (5 and 6)