Cyclitol analogs of biological interest. Regioselective nucleophilic substitutions of 1,4-cyclohexadiene bisepoxide and bisepisulfide

Reaction of cis-1,4-cyclohexadienebisepoxide with aluminium azide afforded the all-equatorial l,3-diazido-4,6-cyclohexanediol (2) through a metal-template mechanism. Hydrogenation of the product gave 2,5-dideoxystreptamine. Synthon 2 underwent normal coupling with 6-deoxy-6-azido-2,3,4-tris(O-benzyl)-α-glucosyl chloride and the resulting product gave the expected glucoside, a precursor of 5-deoxyneamine analogs. The cis- and trans-1,4-cyclohexadienebisepoxides were converted in good yields to the corresponding bisepisulfides and monoepoxide monoepisulfides. Regioselective opening of the cis-bisepisulfide with acetyl chloride and mercuric acetate by a metal-template mechanism led to stereochemically defined dithio analogs of cyclitols.