Radical Glycosylation of Fully Unprotected Sugars

doi:10.6023/cjoc202512042

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (4): 1529-1539.DOI: 10.6023/cjoc202512042 Previous Articles Next Articles

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完全未保护糖的自由基糖基化反应

王钰涓, 朱峰^*(), 杨波^*()

上海交通大学化学化工学院张江高等研究院变革性分子前沿科学中心上海市手性药物分子工程重点实验室上海 200240

收稿日期:2025-12-28 修回日期:2026-01-26 发布日期:2026-03-06
通讯作者: 朱峰, 杨波
基金资助:
科技部重点研发计划(2023YFA1508800); 国家自然科学基金(22301178); 国家自然科学基金(22301180); 国家自然科学基金(22577072); 抗病毒全国重点实验室开放基金(SKLAD-2024-0103)

Radical Glycosylation of Fully Unprotected Sugars

Yujuan Wang, Feng Zhu^*(), Bo Yang^*()

Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Frontiers Science Center for Transformative Molecules (FSCTM), Zhangjiang Institute for Advanced Study, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240

Received:2025-12-28 Revised:2026-01-26 Published:2026-03-06
Contact: Feng Zhu, Bo Yang
Supported by:
National Key R&D Program of China(2023YFA1508800); National Natural Science Foundation of China(22301178); National Natural Science Foundation of China(22301180); National Natural Science Foundation of China(22577072); Open Fund from the State Key Laboratory of Antiviral Drugs(SKLAD-2024-0103)

The recent advances at the forefront of carbohydrate chemistry, with a focus on protecting-group-free glycosylation are reviewed. Carbohydrates are essential biological information carriers, and their synthesis relies critically on efficient glycosylation methods. Traditional approaches often involve laborious protection and deprotection steps, motivating the development of strategies that directly employ natural sugars as feedstocks. Leveraging innovative activation modes such as photocatalysis and radical-mediated pathways, these strategies enable precise, one-step transformations of native sugars into complex glycoconjugates. This approach not only streamlines synthesis and enhances atom economy, but also provides a versatile platform for glycobiology research and glyco-drug development. Here, the application of various unprotected donors in constructing C-, S-, and O-glycosidic bonds is systematically reviewed and the perspectives for future research directions are discussed.

Key words: unprotected glycosyl donors, radical glycosylation, stereoselectivity

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Yujuan Wang, Feng Zhu, Bo Yang. Radical Glycosylation of Fully Unprotected Sugars[J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1529-1539.

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Fig. & Tab. 15

Figure 1. Protecting-group-free synthesis of C-glycosides using glycosyl dithiocarbamates

Figure 2. Photoinduced desulfurative cross-coupling of glycosyl dithioimidocarbonates

Figure 3. Glycosyl radical generation from glycosyl sulfoxides and C-glycoside synthesis

Figure 4. Stereoselective nonenzymatic S-glycosylation of unprotected allyl glycosyl sulfones

Figure 5. DNA-compatible S-glycosylation using unprotected allyl glycosyl sulfones

Figure 6. Unprotected aryl C-glycosides synthesized via allyl glycosyl sulfones

Figure 7. Stereoselective O-glycosylation of carboxylic acids via unprotected allyl glycosyl sulfones

Figure 8. Glycosyl radical formation and reactions from glycosyl sulfinates under acidic conditions

Figure 9. Giese-type carbohydrate-DNA conjugation of glycosyl sulfinates

Figure 10. Giese-type C-glycosylation of glycosyl sulfinates

Figure 11. Direct radical functionalization of native sugars

Figure 12. Site-selective functionalization of unprotected carbohydrates via 4-tetrafluoropyridinylthio activation

Figure 13. Unprotected C-glycosylation of photoredox-activated glycosyl esters

Figure 14. C-Glycosylation of unprotected simple glycosyl benzoates

Figure 15. C—OH bond activation for stereoselective radical C-glycosylation of native saccharides

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完全未保护糖的自由基糖基化反应

Radical Glycosylation of Fully Unprotected Sugars

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