Radical Strategy towards N‐glycosides: Current Advances and Future Prospects

N‐glycosides exhibit diverse biological and pharmacological activities, making their efficient synthesis crucial for both biological research and drug development. Traditional acid‐promoted N‐glycosylation methods, which rely on the formation of oxocarbenium intermediates, often face significant challenges. These methods are water‐sensitive and typically require neighboring group participation to achieve high selectivity. Furthermore, they depend on acid activation, rendering them incompatible with alkyl amine. Additionally, low‐nucleophilicity amides often need to be converted into their TMS‐derivatives to enhance reactivity, limiting the direct use of such substrates. In contrast, radical‐based strategies have emerged as a promising alternative, addressing many of these limitations and leading to notable advances in N‐glycosylation. This review explores the unique properties of N‐glycosides, the inherent challenges of traditional N‐glycosylation techniques, and the transformative advantages offered by radical‐based approaches. Specifically, it highlights recent advancements in radical‐mediated N‐glycosylation, including photoredox radical strategies, radical/ionic hybrid approaches, and metallophotoredox catalysis, accompanied by a detailed discussion of the underlying mechanisms. Finally, the ongoing challenges and potential future directions of N‐glycoside synthesis using radical strategies are presented.