Models for Glycoside Hydrolysis. Synthesis and Hydrolytic Studies of the Anomers of a Conformationally Rigid Acetal

Article abstract of DOI:10.1021/jo01311a018

The methyl acetals of 2-hydroxy-3-oxa-trans-decalin were synthesized as models for conformationally rigid methyl glycosides.The compounds were prepared by Baeyer-Villiger oxidation of trans-hexahydrohydrindan-2-one followed by reduction of the resulting lactone with diisobutylaluminum hydride.Treatment of the hemiacetal with methanol and an acid catalyst afforded a mixture of acetals which were separated by chromatography and identified by NMR.Hydrolytic studies were carried out under a range of acid concentrations and temperatures.The mechanistic implications of the relative hydrolysis rates (axial/equatorial ratio of 1.51+/-0.22) and activation parameters are discussed.