Preparation of the α-glucosides11, 12, 13and14were accomplished through glycosylation of racemictrans-1-hydroxy-2-(hydroxymethyl)cyclohexane using 2-thiopyridyl tetra-O-benzyl-glucoside as the glycosyl donor in acceptable overall yield for α-selectivity, but with poor regioselectivity. Glycosylation under thermodynamic control using tetrabenzyl glucopyranose acetate and trimethylsilyl triflate as the promotor gave similar results. The unprotected glucosides12and13were separated and characterized by NMR spectroscopy. Similarly methyl 4-deoxy-α-isomaltoside (5a) was prepared through halide catalyzed glycosylation of methyl 2,3-di-O-benzoyl-4-deoxy-α-D-glucopyranoside (15) in acceptable yield and the unprotected compound characterized by NMR spectroscopy. Compounds5a, 12a, 13aand the mixture11aand14awere all tested as substrates for the enzyme glucoamylase fromAspergillus nigerand proved to be very poor substrates for the enzymic hydrolysis.