A concise and stereospecific synthesis of some cyclitols containing eight-membered rings: cyclooctane-1,2,3,4-tetraoles

A concise and efficient synthesis of cyclooctane-1,2,3,4-tetraoles, new polyhydroxylated eight-membered carbocycles, is described starting from cis, cis -1,3-cyclooctadiene. Cyclooctene endoperoxide obtained by photooxygenation of cis, cis -1,3-cyclooctadiene was the key compound in the synthesis. Reduction of the endoperoxide with zinc or thiourea followed by acetylation of the hydroxyl group and OsO 4 /NMO oxidation of the double bond gave (1 R ( S ),2 S ( R ),3 R ( S ),4 S ( R ))-cyclooctane-1,2,3,4-tetraol. Interestingly, epoxidation of cyclooctene-1,4-diol with m -CPBA also afforded trans -epoxy-diol 17. (1 R ( S ),2 R ( S ),3 R ( S ),4 S ( R ))-cyclooctane-1,2,3,4-tetraol was easily obtained by hydrolysis of epoxy-diol 17.