You Zou, Hengfu Xu, Cang‐Xin Zheng, Weiwei Zhang, Xin‐Shan Ye, De‐Cai Xiong
The effective construction of structurally homogeneous glycosides is requisite in oligosaccharide assembly and the development of carbohydrate-based drugs. A fluorine-mediated stereoselective Ferrier-type glycosylation is reported herein. Glycals are pre-decorated with photo-2-difluoroalkylation and reacted with diverse acceptors to obtain exclusively α-selective Ferrier rearrangement products. This procedure can tolerate extensive substrates and achieve good yields. Subsequent gram-scale and oligosaccharide syntheses further demonstrate the applicability and practicality of this strategy. Detailed density functional theory studies demonstrate the predominant stereoselectivity of the glycosylation process.