完全未保护糖的自由基糖基化反应

doi:10.6023/cjoc202512042

有机化学 ›› 2026, Vol. 46 ›› Issue (4): 1529-1539.DOI: 10.6023/cjoc202512042 上一篇下一篇

综述与进展

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)

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摘要/Abstract

综述了糖化学前沿领域的最新研究进展, 重点聚焦于无保护糖的糖苷化反应. 糖类是重要的生物信息分子, 其合成高度依赖高效的糖苷化方法. 传统策略通常包括繁琐的保护及脱保护步骤, 进一步推动了以天然糖为原料直接进行糖苷化反应策略的发展. 借助光催化和自由基介导等新型活化方式, 这类策略可将天然无保护糖一步精准转化为复杂糖缀合物. 这种新型活化方式不仅简化了合成步骤, 提高了原子经济性, 还为糖生物学研究与糖类药物开发提供了通用平台. 系统综述了各类无保护糖基供体在构建C-糖苷, S-糖苷与O-糖苷键中的应用, 并对未来研究方向进行了展望.

关键词: 无保护糖基供体, 自由基糖苷化反应, 立体选择性

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

引用此文

王钰涓, 朱峰, 杨波. 完全未保护糖的自由基糖基化反应[J]. 有机化学, 2026, 46(4): 1529-1539.

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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图/表 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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