Stereoselective Ferrier-Type O-Glycosylation Enabled by Difluoromethylated Glycal Donors
You Zou1, Hengfu Xu1, Cang-Xin Zheng1
1State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Xue Yuan Road No. 38, Beijing, 100191, China.
Abstract:
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.
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