C-glycosylation through the formation of glycosyl radical is a very feasible and expedient approach for making of the C–C anomeric bond. In this light, this review article is covering selected literature from 2000 to 2022 on the synthetic development of C-glycosylation involving the generation of glycosyl radical as a crucial intermediate in a stereoselective fashion. The generation of glycosyl radical is controlled by the reaction method applying to the radical precursor. Those methods are categorized in terms of a key source of an initiator such as metal-free activation of radical precursor, photochemical induced approach, and metal-mediated approach including transition metal-mediated, lanthanide, and non-transition metal-mediated approach with brief mechanistic discussion, and stereochemical outcome of resultant C-glycosides in detail. This brief discussion accumulates the stereoselective synthesis of challenging C-linked building blocks in a more facile way via generation of glycosyl radical and those building blocks have a great role as drugs, inhibitors, glycoconjugates in the field of biological and medicinal chemistry.

C-glycosylation through the formation of glycosyl radical is a very feasible and expedient approach for making of the C–C anomeric bond. In this light, this review article is covering selected literature from 2000 to 2022 on the synthetic development of C-糖基化涉及糖基自由基的产生，作为立体选择性方式中的关键中间体。糖基自由基的产生由应用于自由基前体的反应方法控制。这些方法根据引发剂的关键来源进行分类，例如自由基前体的无金属活化、光化学诱导方法和金属介导方法，包括过渡金属介导、镧系元素和非过渡金属介导方法，并简要介绍生成的C-糖苷的详细机理讨论和立体化学结果。这个简短的讨论积累了具有挑战性的C-的立体选择性合成通过产生糖基自由基以更容易的方式连接构建单元，这些构建单元在生物和药物化学领域作为药物、抑制剂、糖缀合物具有重要作用。