The solvolysis of epoxycarbinyl substrates 1 has been the subject of several mechanistic studies. In spite of these investigations, it has not been established whether these solvolysis reactions proceed with anchimeric assistance from the epoxide oxygen and involve an oxabicyclobutonium ion intermediate or whether unassisted solvolysis occurs. Conflicting data in the literature suggest that the ability of the epoxide oxygen to provide anchimeric assistance is dependant upon structural and electronic features of the epoxycarbinyl substrate in question. The aim of this project was to study the nucleophilic substitution reactions of tetrahydrofurfuryl and tetrahydropyranyl sulfonates 2a and 2b as well as cyclopentylmethyl and cyclohexylmethyl sulfonates 3a and 3b, respectively, to probe the effect of a neighboring oxygen on solvolyses rates and product distribution. The rates of solvolyses of cyclopentylmethyl tosylate and tetrahydrofuranomethyl tosylate have been compared to determine if the oxygen lends anchimeric assistance to the leaving group in the solvolyses reactions of the latter. This research has led to an increased understanding of the role of the ether oxygen in reaction of tetrahydrofurfuryl tosylate.



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