Hydrolysis of α- and β-Glycosides. New Experimental Data and Modeling of Reaction Pathways

[reaction: see text] The cyclization of oxocarbenium ion conformers 6alpha and 6beta (from 11E and 11Z) gave only the beta-glycoside 1beta, and the addition of methanol to the oxocarbenium ion 3 yielded mainly the alpha-glycoside 1alpha with both experiments being carried out under kinetically controlled conditions. RHF/6.31G calculations reproduce well these experimental results and show that the endocyclic and the exocyclic C-O bond cleavage processes can compete in the hydrolysis of 1beta, whereas 1alpha gets hydrolyzed by exocyclic C-O bond cleavage only.