Advances in Glycosylation Reactions Promoted by Trivalent Iodine Reagents★

doi:10.6023/cjoc202507032

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (9): 3148-3162.DOI: 10.6023/cjoc202507032 Previous Articles Next Articles

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三价碘试剂促进的糖苷化反应研究进展^★

谭玉林^a, 梁志华^a, 陈薇^b, 孟令奎^a^,^*(), 曾静^a^,^*(), 万谦^a^,^*()

^a 华中科技大学同济医学院药学院武汉 430030
^b 华中科技大学同济医学院附属协和医院药学部武汉 430022

收稿日期:2025-07-23 修回日期:2025-08-28 发布日期:2025-09-11
基金资助:
国家自然科学基金(22177034); 国家自然科学基金(22025102); 国家自然科学基金(22301089)

Advances in Glycosylation Reactions Promoted by Trivalent Iodine Reagents^★

Yulin Tan^a, Zhihua Liang^a, Wei Chen^b, Lingkui Meng^a^,^*(), Jing Zeng^a^,^*(), Qian Wan^a^,^*()

^a School of Pharmacy, Tongji Medical College, Huazhong University of Science and Technology, Wuhan 430030
^b Department of Pharmacy, Union Hospital, Tongji Medical College, Huazhong University of Science and Technology, Wuhan 430022

Received:2025-07-23 Revised:2025-08-28 Published:2025-09-11
Contact: *E-mail: wanqian@hust.edu.cn; menglk@hust.edu.cn; zengjing0052@hust.edu.cn
About author:
^★ Academic Papers of the 27^th Annual Meeting of the China Association for Science and Technology.
Supported by:
National Natural Science Foundation of China(22177034); National Natural Science Foundation of China(22025102); National Natural Science Foundation of China(22301089)

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

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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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Fig. & Tab. 18

Scheme 1. PhIO/acid-mediated activation of thioglycosides

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

Scheme 3. Trivalent iodines/acid mediated activation of thioglucoside

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

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

Scheme 6. N-Glycosylation mediated by PIFA/acid

Scheme 7. Thioglycoside activation promoted by trivalent iodonium salts

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

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

Scheme 10. PhIO promoted glycosylation with selenoglycosides

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

Scheme 12. PIFA/PhIO promoted glycosylation with selenoglycosides

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

Scheme 14. PIFA or PIDA-mediated synthesis of azidoglycosides

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

Scheme 16. Phenylselenoglycosylation mediated by PIFA

Scheme 17. Continuous flow synthesis of azidophenylselenoglycosides

Scheme 18. Togni-II-mediated by thioglycosides synthesis

References 62

[1]	Willgerodt, C. J. Prakt. Chem. 1886, 33, 154.
[2]	Wirth, T. Top. Curr. Chem. 2003, 224.
[3]	Zhdankin, V. V. Hypervalent Iodine Chemistry: Preparation, Structure and Synthetic Application of Polyvalent Iodine Compounds, John Wiley & Sons Ltd, Chichester, UK, 2014
[4]	Kaiho, T. Iodine Chemistry and Applications, John Wiley & Sons, Inc., Chichester, UK, 2015.
[5]	Wirth, T. Top. Curr. Chem. 2016, 373.
[6]	Olofsson, B.; Marek, I.; Rappoport, Z. Patai’s Chemistry of Functional Groups: The Chemistry of Hypervalent Halogen Compounds, Wiley, Chichester, UK, 2019.
[7]	Kirschning, A. Eur. J. Org. Chem. 1998, 2267.
[8]	Yoshimura, Y.; Wakamatsu, H.; Natori, Y.; Saito, Y.; Minakawa, N. Beilstein. J. Org. Chem. 2018, 14, 1595. doi: 10.3762/bjoc.14.137 pmid: 30013687
[9]	Upadhyaya, K.; Dubbu, S. Carbohydr. Res. 2024, 542, 109175.
[10]	Mahanti, M.; Pal, K. B.; Wallentin, C. J.; Galan, M. C. Chem.-Eur. J. 2024, No. e202400087.
[11]	Xiao, X.; Zhao, Y.; Shu, P.; Zhao, X.; Liu, Y.; Sun, J.; Zhang, Q.; Zeng, J.; Wan, Q. J. Am. Chem. Soc. 2016, 138, 13402.
[12]	Meng, L.; Wu, P.; Fang, J.; Xiao, Y.; Xiao, X.; Tu, G.; Ma, X.; Teng, S.; Zeng, J.; Wan, Q. J. Am. Chem. Soc. 2019, 141, 11775.
[13]	Xiao, X.; Zeng, J.; Fang, J.; Sun, J.; Li, T.; Song, Z.; Cai, L.; Wan, Q. J. Am. Chem. Soc. 2020, 142, 5498.
[14]	Sun, J.; Fang, J.; Xiao, X.; Cai, L.; Zhao, X.; Zeng, J.; Wan, Q. Org. Biomol. Chem. 2020, 18, 3818.
[15]	Zhao, Y.; Zeng, J.; Liu, Y.; Xiao, X.; Sun, G.; Sun, J.; Shu, P.; Fu, D.; Meng, L.; Wan, Q. J. Carbohydr. Chem. 2018, 37, 471.
[16]	Chen, W.; Zeng, J.; Liao, Z.; Teng, S.; Xiao, X.; Meng, L.; Wan, Q. J. Carbohydr. Chem. 2018, 37, 498.
[17]	Xu, Y.; Zhang, Q.; Xiao, Y.; Wu, P.; Chen, W.; Song, Z.; Xiao, X.; Meng, L.; Zeng, J.; Wan, Q. Tetrahedron Lett, 2017, 58, 2381.
[18]	Cai, L.; Zeng, J.; Li, T.; Xiao, Y.; Ma, X.; Xiao, X.; Zhang, Q.; Meng, L.; Wan, Q. Chin. J. Chem. 2020, 38, 43.
[19]	Zhao, X.; Cai, L. Chin. J. Chem. 2020, 38, 220.
[20]	Teng, S.; Meng, L.; Xu, B.; Tu, G.; Wu, P.; Liao, Z.; Tan, Y.; Guo, J.; Zeng, J.; Wan, Q. Chin. J. Chem. 2021, 39, 3429.
[21]	Zhang, J.; Liu, H.; Teng, S.; Liao, Z.; Meng, L.; Wan, Q.; Dong, S. Chem. Commun. 2023, 59, 6513.
[22]	Mahanti, M.; Pal, K. B.; Wallentin, C. J.; Galan, M. C. Chem.-Eur. J. 2024, e202400087.
[23]	Tsai, T. Y. R.; Jin, H.; Wiesner, K. Can. J. Chem. 1984, 62, 1403.
[24]	Garegg, P. J.; Henrichson, C.; Norberg, T. Carbohydr. Res. 1983, 116, 162.
[25]	Van Cleve, J. W. Carbohydr. Res. 1979, 70, 161.
[26]	Dondoni, A.; Marra, A.; Massi, A. Angew. Chem., Int. Ed. 2005, 44, 1672.
[27]	Sato, S.; Mori, M.; Ito, Y.; Ogawa, T. Carbohydr. Res. 1986, 155, C6.
[28]	Veeneman, G. H.; Van Leeuwen, S. H.; Van Boom, J. H. Tetrahedron Lett. 1990, 31, 1331.
[29]	Takeuchi, K.; Tamura, T.; Mukaiyama, T. Chem. Lett. 2000, 29, 124.
[30]	Qin, Z. H.; Li, H.; Cai, M. S.; Li, Z. J. Carbohydr. Res. 2002, 337, 31.
[31]	Fukase, K.; Hasuoka, A.; Kinoshita, I.; Kusumoto, S. ; Tetrahedron Lett. 1992, 33, 7165.
[32]	Fukase, K.; Kinoshita, I.; Kanoh, T.; Nakai, Y.; Hasuoka, A.; Kusumoto, S. Tetrahedron 1996, 52, 3897.
[33]	Kajimoto, T.; Morimoto, K.; Ogawa, R.; Dohi, T.; Kita, Y. Eur. J. Org. Chem. 2015, 2138.
[34]	Morimoto, K.; Yanase, K.; Kajimoto, T.; Kita, Y. Org. Lett. 2022, 24, 9028. doi: 10.1021/acs.orglett.2c03661 pmid: 36455214
[35]	Kurz, T.; Morimoto, K.; Kita, Y.; Kajimoto, T. ARKIVOC 2021, 2021, 164.
[36]	Kolb, H. C.; Finn, M. G.; Sharpless, K. B. Angew. Chem., Int. Ed. 2001, 40, 2004.
[37]	Mandoli, A. Molecules 2016, 21, 1174.
[38]	Chu, A. H.; Minciunescu, A.; Montanari, V.; Kumar, K.; Bennett, C. S. Org. Lett. 2014, 16, 1780.
[39]	Chu, A. H.; Minciunescu, A.; Bennett, C. S. Org. Lett. 2015, 17, 6262.
[40]	Saliba, R. C.; Wooke, Z. J.; Nieves, G. A.; Chu, A. H. A.; Bennett, C. S.; Pohl, N. L. B. Org. Lett. 2018, 20, 800. doi: 10.1021/acs.orglett.7b03940 pmid: 29336575
[41]	Sun, A.; Liu, T.; Li, Z.; Meng, S.; Meng, X.; Li, Z.; Li, Z. Org. Lett. 2024, 26, 2478. doi: 10.1021/acs.orglett.4c00653 pmid: 38501865
[42]	Mamidyala, S. K.; Finn, M. G. J. Org. Chem. 2009, 74, 8417. doi: 10.1021/jo901857x pmid: 19827757
[43]	Du, Y.; Gu, G.; Wei, G.; Hua, Y.; Linhardt, R. J. Org. Lett. 2003, 5, 3627.
[44]	Yang, T.; Zhu, F.; Walczak, M. A. Nat. Commun. 2018, 9, 3650.
[45]	Kita, Y.; Yasuda, H.; Tamura, O.; Itoh, F.; Tamura, Y. Tetrahedron Lett. 1984, 25, 4681.
[46]	Kita, Y.; Tamura, O.; Yasuda, H.; Itoh, F.; Tamura, Y. Chem. Pharm. Bull. 1985, 33, 4235.
[47]	Nishizono, N.; Baba, R.; Nakamura, C.; Oda, K.; Machida, M. Org. Biomol. Chem. 2003, 1, 3692. pmid: 14649900
[48]	Nishizono, N.; Akama, Y.; Agata, M.; Sugo, M.; Yamaguchi, Y.; Oda, K. Tetrahedron. 2011, 67, 358.
[49]	Nishizono, N.; Soma, K.; Baba, R.; Machida, M.; Oda, K. Heterocycles 2008, 75, 619.
[50]	Taniike, H.; Inagaki, Y.; Matsuda, A.; Minakawa, N. Tetrahedron 2011, 67, 7977.
[51]	Ishii, K.; Saito-Tarashima, N.; Ota, M.; Yamamoto, S.; Okamoto, Y.; Tanaka, Y.; Minakawa, N. Tetrahedron 2016, 72, 6589.
[52]	Shi, L.; Kim, Y. J.; Gin, D. Y. J. Am. Chem. Soc. 2001, 123, 6939. pmid: 11448206
[53]	Chennaiah, A.; Bhowmick, S.; Vankar, Y. D. RSC Adv. 2017, 7, 41755.
[54]	Islam, M.; Tirukoti, N. D.; Nandi, S.; Hotha, S. J. Org. Chem. 2014, 79, 4470.
[55]	Reddy, T. R.; Rao, D.S.; Babachary, K.; Kashyap, S. Eur. J. Org. Chem. 2016, 291.
[56]	Meng, S.; Zhong, W.; Yao, W.; Li, Z. Org. Lett. 2020, 22, 2981.
[57]	Tingoli, M.; Tiecco, M.; Chianelli, D.; Balducci, R.; Temperini, A. J. Org. Chem. 1991, 56, 6809.
[58]	Santoyo-Gonzalez, F.; Calvo-Flores, F. G.; Garcia-Mendoza, P.; Hernandez-Mateo, F.; Isac-Garcia, J.; Robles-Diaz, R. J. Org. Chem. 1993, 58, 6122.
[59]	Czernecki, S.; Ayadi, E.; Randriamandimby, D. J. Org. Chem. 1994, 59, 8256.
[60]	Mironov, Y. V.; Sherman, A. A.; Nifantiev, N. E. Tetrahedron Lett. 2004, 45, 9107.
[61]	Guberman, M.; Pieber, B.; Seeberger, P. H. Org. Process Res. Dev. 2019, 23, 2764. doi: 10.1021/acs.oprd.9b00456
[62]	Eisenberger, P.; Gischig, S.; Togni, A. Chem. Eur. J. 2006, 12, 2579.

三价碘试剂促进的糖苷化反应研究进展^★

Advances in Glycosylation Reactions Promoted by Trivalent Iodine Reagents^★

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三价碘试剂促进的糖苷化反应研究进展★

Advances in Glycosylation Reactions Promoted by Trivalent Iodine Reagents★

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PDF

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Abstract

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Fig. & Tab. 18

References 62

Related Articles 15

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三价碘试剂促进的糖苷化反应研究进展^★

Advances in Glycosylation Reactions Promoted by Trivalent Iodine Reagents^★