三价碘试剂促进的糖苷化反应研究进展★

doi:10.6023/cjoc202507032

摘要/Abstract

三价碘化合物凭借其独特的三中心四电子键结构, 展现出与Hg(II)、Tl(III)、Pb(IV)等重金属相似的化学特性, 同时兼具环境友好、低毒性的优势, 符合绿色化学的发展理念, 因而在有机合成领域引起了广泛的研究兴趣. 近三十余年来, 三价碘试剂的应用在糖化学研究领域取得了显著进展, 为糖苷键的高效构建提供了创新性的解决方案. 系统综述了三价碘试剂促进的糖苷化反应的研究进展, 根据糖基给体类型的不同, 分别阐述了其对硫苷、硒苷、锡苷以及烯糖等的活化作用及其糖苷化反应. 重点讨论了三价碘试剂活化糖基给体的作用机制、糖苷化反应的底物适用范围, 并对该领域未来的发展方向和应用前景进行了展望.

关键词: 三价碘试剂, 糖苷化反应, 硫苷, 烯糖

Trivalent iodine compounds have attracted extensive research interest in organic synthesis due to their chemical properties resembling those of heavy metals, such as Hg(II), Tl(III), and Pb(IV), while being free from the toxicity associated with such metals. Over the past three decades, chemists have been exploring the application of trivalent iodine reagents to address the construction of glycosidic bonds. This review summarizes the progress in trivalent iodine-promoted glycosylation reactions, categorized by the activation of different glycosyl donors, including thioglycosides, selenoglycosides, stannyl glycosides, and glycal donors. The activation mechanism of glycosyl donors with trivalent iodine reagents and the scope of glycosylation substrates are discussed. Additionally, current challenges are addressed, and an outlook for future research is provided.

Key words: trivalent iodine, glycosylation, thioglycoside, glycal

引用此文

谭玉林, 梁志华, 陈薇, 孟令奎, 曾静, 万谦. 三价碘试剂促进的糖苷化反应研究进展^★[J]. 有机化学, 2025, 45(9): 3148-3162.

Yulin Tan, Zhihua Liang, Wei Chen, Lingkui Meng, Jing Zeng, Qian Wan. Advances in Glycosylation Reactions Promoted by Trivalent Iodine Reagents^★[J]. Chinese Journal of Organic Chemistry, 2025, 45(9): 3148-3162.

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图/表 18

图式1. 亚碘酰苯与酸介导的硫苷供体活化

Scheme 1. PhIO/acid-mediated activation of thioglycosides

图式2. PIFA与酸介导的2-氨基糖硫苷供体活化

Scheme 2. PIFA/acid mediated glycosylation of 2-aminothioglycoside

图式3. 不同三价碘试剂与酸介导的葡萄糖硫苷供体活化

Scheme 3. Trivalent iodines/acid mediated activation of thioglucoside

图式4. 不同三价碘试剂与BF3•Et2O介导的葡萄糖硫苷供体酯糖苷化

Scheme 4. Trivalent iodines/BF3•Et2O mediated activation of thioglucoside

图式5. 基于三价碘试剂促进的硫苷活化的复杂寡糖一锅合成

Scheme 5. One-pot synthesis of complex oligosaccharides via trivalent iodines mediated thioglucoside activation

图式6. PIFA与酸介导的氮糖基化

Scheme 6. N-Glycosylation mediated by PIFA/acid

图式7. 三价碘盐促进的硫苷活化

Scheme 7. Thioglycoside activation promoted by trivalent iodonium salts

图式8. 三价碘盐促进的硫苷活化选择性糖苷化

Scheme 8. Thioglycoside activation selective glycosylation promoted by trivalent iodonium salts

图式9. 三价碘盐促进的寡糖液相自动化合成

Scheme 9. Automated solution-phase oligosaccharide synthesis promoted by trivalent iodonium salts

图式10. 亚碘酰苯促进的硒苷活化

Scheme 10. PhIO promoted glycosylation with selenoglycosides

图式11. PhIO/PhI(OH)OTs介导的锡苷糖苷化反应

Scheme 11. PhIO/PhI(OH)OTs mediated glycosylation of stannyl glycosides

图式12. PIFA/PhIO促进的硫/硒代糖活化

Scheme 12. PIFA/PhIO promoted glycosylation with selenoglycosides

图式13. PIDA/BF3•Et2O介导的烯糖糖苷化

Scheme 13. PIDA/BF3•Et2O mediated glycosylation of glycals

图式14. PIFA或PIDA介导的叠氮糖苷的合成

Scheme 14. PIFA or PIDA-mediated synthesis of azidoglycosides

图式15. 三价碘试剂介导的2-碘代-2脱氧糖苷的合成

Scheme 15. Synthesis of 2-iodo-2-deoxyglycosides mediated by trivalent iodine reagents

图式16. PIFA介导的苯硒基糖苷化反应

Scheme 16. Phenylselenoglycosylation mediated by PIFA

图式17. 叠氮苯硒基糖苷的连续流动相合成

Scheme 17. Continuous flow synthesis of azidophenylselenoglycosides

图式18. Togni-II介导的S-糖苷的合成

Scheme 18. Togni-II-mediated by thioglycosides synthesis

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