On Five-vs Six-membered Diacetal Formation from Threitol and the Intermediacy of Unusually Stable Protonated Species1 Academic Article uri icon


  • The long known, but hitherto poorly understood, thermodynamically controlled diacetalation of rac-threitol with alkylaldehydes provided bicyclic, cis-tetraoxadecalin (TOD)(“66”) and bi (dioxolanyl)(BDO)(“55”) products, shown to be formed in acid-concentration and temperature-dependent ratio. The configurational and conformational isomeric diacetals obtained in four such reactions of substituted aldehydes (RCHO, R= CH3, CH2Cl, CH2Br, CO2CH3) with rac-threitol were isolated and characterized. A variable acid-concentration analysis of the equilibrium mixture of products in one such case (R= CH2Br) was performed and provided equilibrium constants and, hence, free-energy differences among these products and their relatively stable protonated intermediates. The latter were rationalized by the unusually high proton-affinity calculated for the cis-TOD (“66”) form.

publication date

  • March 24, 2000