Abstract
Abstract Synthesis and solvolytic behavior of derivatives of the highly hindered title compounds are described, exo-Tricyclo[4.4.1.12,5]dodeca-3,7,9-trien-syn-yl tosylate (syn-18-OTs) and the corresponding perhydro derivative, syn-23-OTs, solvolyze at rates that are in reasonable agreement with those predicted by Foote-Schleyer calculations.syn-18-OTs, and its dihydro derivatives, syn-19-OTs and syn-20-OTs, give completely rearranged products on solvolysis in acetic acid and 75% dioxane, 80% acetone, and 75% dioxane, respectively (Table 2). These products can be explained by normal cationic rearrangements, probably occurring after ionization. On the other hand, anti-18-OTs and anti-23-OTs solvolyze at rates ca. 102 times slower than those predicted by Foote-Schleyer calculations. Presumably the anti derivatives of 18-OTs, 20-OTs, 23-OTs, and the tetrahydro tosylate (22-OTs) suffer steric hindrance to ionization. Product formation from anti-18-OTs (Table 3) and anti-19-OTs in acetic acid and 75% dioxane, respectively, is explained as a [3s+3s] sigmatropic shift induced by ionization, with formation of an allylic ion providing the driving force for rearrangement.
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