Described herein is the first application of perfluorinated solvent in the stereoselective formation of O-/S-glycosidic linkages that occurs via a Ferrier rearrangement of acetylated glycals. In this system, the weak interactions between perfluoro-n-hexane and substrates could augment the reactivity and stereocontrol. The initiation of transformation requires only an extremely low loading of resin-H+ and the mild conditions enable the accommodation of a broad spectrum of glycal donors and acceptors. The ‘green’ feature of this chemistry is demonstrated by low toxicity and easy recovery of the medium, as well as operational simplicity in product isolation.

Carbohydrates are not only an energy source for life activities, but also play a vital role in many physiological activities and drug development. Glycosylation is the core reaction of carbohydrate chemistry, and it is still a big challenge to develop a general stereoselective and efficent glycosylation method. The control of stereoselectivity is mainly carried out from three aspects: glycosyl donors, catalytic conditions and glycosyl acceptors. Among them, the development of glycosyl donors is the most concerned. The development of functional group of glycosyl donors on stereoselective regulation in the past decades is summarized. According to the way in which the functional groups participate in the glycosylation reactions, they are divided into neighboring-group participating groups, remote group participating groups, intramolecular aglycone delivery groups, coordination functional groups and hydrogen-bonding mediated groups.