Cyclic Sulfates: Useful Substrates for Selective Nucleophilic Substitution.

The reactions of cyclic sulfates were studied with fluoride ion, phenoxide ion, and high specific activity [ 18 F] fluoride. Cyclic sulfates of low molecular weight acyclic diols were produced by synthesis and permanganate oxidation of the corresponding sulfites. The sulfites were not good substrates for substitution. Cyclic sulfates containing five-, six-, and seven-membered rings were included. The nucleophilic reactions on cyclic sulfates are sensitive to steric and electronic direction. Steric direction of phenoxide was nearly completely regiospecific, and incorporation of fluoride showed pronounced regioselectivity. Sulfates of cyclic diols showed the greatest degree of steric control. The cyclic sulfate group appears to be a generally useful means of simultanously facilitating nucleophilic reactions and protecting nearby hydroxyl functions