Szrmmary. In buffered 70% aqueous dioxanc the cyclopropylcarbinyl (1-X), edo-cyclobutyl (2-X) and homoallylic (3-X) derivatives (X = nucleofuge) react t o give the same mixture of alcohols 1-OH and 3-OH by way of a common intermediate, the symmetrical homoallylic ion 22. This tollows from a study of optically active reactants 1-X and 3-X and from the deuterium scrambling pattern in the products from deuteriated 1-S, eizdo-2-X and 3-X. The high solvolysis rates of 3-X indicate n-bond participation in the transition state, while the high rates of 1-X and endo-2-X reflect strong o-bond participation which is abscnt in exo-2-X.Prolonged heating of 1-X, endo-2-X and 3-X in formic acid leads to a degenerate rearrangcment of the initially formed 3-formate. As evidenced by deuterium scrambling, carbon atoms 1, 3 and 7 eventually become positionally equivalent in the latter compound.
1.Introduction. -The interconversion of cyclopropylcarbinyl-, cyclobutyland homoallylic derivativesla), such as the compounds 1, endo-and ex03 and 3 (X = nucleofuge) in solvolytic reactions has continued to attract widespread attention. a s is evident from recent review articles [l] research in this area has tended to concentrate on the still controversial nature and number of intermediates involved in the rearrangementsz) .
Tricyclo[3.2.1.02,7]octan‐3‐ol (1) and its 4‐isomer 7 were obtained by hydroboration of tricyclo[3.2.1.02,7]oct‐3‐ene (5). The former alcohol 1 is quantitatively converted to the isomeric alcohol exo‐bicyclo[3.2.1]oct‐2‐en‐7‐ol (3) by treatment with aqueous acid.
Photolysis of 1‐diazo‐3‐(cyclopent‐3‐enyl)‐propan‐2‐one (12c) gave a high yield of tricyclo[3.2.1.03,6]octan‐4‐one (10a). Reduction of the latter ketone produced a mixture of endo‐ and exo‐tricyclo[3.2.1.03,6]octan‐4‐ol 2 and 9, respectively. Oxidation of these secondary alcohols with silver carbonate in benzene furnished a mixture of the ketone 10a and the lactone 14 of 6‐hydroxy‐bicyclo[2.1.1]heptane‐2‐carboxylic acid. The latter is thought to be formed by oxydation of the hydrate of the strained ketone 10a.
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