Steric Effect in Regioselective Cyclization of 3,4-Epoxy Alcohols to Oxetanes

A number of 3,4-epoxy alcohols, involving critical structural factors for oxetane formation by intramolecular cyclization, were prepared and treated with base under aqueous (KOH in 75% aq DMSO) and anhydrous conditions (NaH in THF). The result of the reactions of cis- and trans-4,5-epoxy-2-rnethyl-2-undecanols, coupled with that of 1-(2,3-epoxybutyl)- and 1-(2,3-epoxy-3-methylbutyl)-1-cyclohexanols (1a and 1b), indicated that the regioselective oxetane formations of 3,4-epoxy alcohols with alkoxide anions are much insensitive to steric hindrance at the attacked oxirane rings, compared with the corresponding reactions with carbanions, while that of 1-(2,3-epoxypropyl)-1-cycloalkanols revealed that the relevant reactions depend on bulkiness of attacking alkoxide anions. Moreover, the result of the reactions of 1-(1,2-epoxycycloalkyl)-2-methyl-2-propanols under the aqueous conditions demonstrated that the oxetane formations are affected seriously by steric hindrance at the attacked oxirane rings, although th...

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