期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 65, 期 6, 页码 1636-1642出版社
AMER CHEMICAL SOC
DOI: 10.1021/jo9908952
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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.
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