1,2-Anhydroglucose6reacts smoothly and with a high degree of stereoselectivity with a variety of carboxylic and phosphoric acids resulting in the formation of the predominantly β-oriented 1-O-acyl and 1-O-phosphorylglucoses7-17. This methodology has been successfully applied in the construction of glycolipids1a,b. Ring-opening of the 1,2-anhydroglucose derivative19with benzoic acid furnished exclusively the β-aligned key intermediate20. Subsequent ICDT-assisted chemoselective α-glucosylation of20with thioethyl donor21, followed by glycosidation of kojibiosyl benzoate22with glycerol acceptor23gave the fully protected α-diglucosyl glycerol derivative25, which upon desilylation (→28), acylation (→29 or 30) and deprotection afforded the target glycolipids1a-bin high overall yield.