AbstractTwo CH3groups at C(6) of 2‐exo‐ (10a) and 2‐endo‐norbornylp‐toluenesulfonate11alower their solvolysis rates in 80% EtOH by factors of 28 and 16, respectively. A spirocyclopropyl group including C(6), as in21aand22a, reduces the rate ofexo‐ andendo‐ionization by factors of 250 and 8, respectively. The geminally dimethyl‐substituted tosylates10aand11ayield the 2‐exo‐alcohol10b, whereas the spirocyclopropyl‐substituted tosylates21aand22afurnish rearranged 3‐brendanol23. These findings are readily rationalized by the inductive model, according to which norbornyl cation formation is controlled by the inductive effect