Aromatic protective groups are widely used in carbohydrate synthesis owing to their numerous merits. However, they unpredictably make certain compounds insoluble in organic solvents owing to their π-stacking abilities. It was found that introducing a tert-butyl group onto the aryl moiety improves the solubility of highly insoluble carbohydrate derivatives, such as those of N-acetylglucosamine. In this study, tert-butyl-substituted aromatic protecting groups are demonstrated to work as well as the original unsubstituted form, while improving the efficiency of glycosylations.