Stereoselective Synthesis of 2‐Deoxy‐α‐N‐Glycosides from Glycals with 1,4,2‐Dioxazol‐5‐ones

Comprehensive Summary The synthesis of N ‐glycosides has received significant attention due to their crucial role in carbohydrate chemistry. Despite considerable advancements developed in the construction of N ‐glycosides, methods for the stereoselective construction of 2‐deoxy‐ α ‐ N ‐glycosides are still limited. Herein, we disclosed a nickel‐catalyzed hydroamination of glycals under mild conditions. This transformation could allow for the stereoselective synthesis of an array of 2‐deoxy‐ α ‐ N ‐glycosides with excellent α ‐stereoselectivity. Nickel‐catalyzed glycosylation reactions, particularly those involving anomeric C(sp 3 )‐metal bond formation, have proven to be an effective and stereoselective strategy for producing various N ‐glycosides. Additionally, with highlight of the application of this reaction, γ‐sugar amino acid derivatives were synthesized.