SYNTHESIS OF 2-THIABICYCLO[2.2.1]HEPTANE DERIVATIVES

The addition of thiophosgene to cyclopentadiene provided 3,3-dichloro-2-thiabicyclo[2.2.1]hept-5-ene (5) which was converted into the more stable sulfone 7 by oxidation with m-chloroperbenzoic acid. Catalytic hydrogenation of the dichloro sulfone 7 resulted in the formation of the saturated monochloro sulfone 13 which was subsequently reduced to the parent sulfide 12 with lithium aluminum hydride. Reduction of sulfone 7 with chromous ion in aqueous acetone followed by lithium aluminum hydride provided 2-thiabicyclo [2.2.1] hept-5-ene (10). The alcohol, exo-5-hydroxy-2-thiabicyclo [2.2.1]heptane, was prepared by a multistep sequence from 4-hydroxycyclopentene. © 1969, American Chemical Society. All rights reserved.