Thiocrown Ether: Reversing SN1 to SN2 Pathways in 1,2-cis Phosphoryl Glycosylation
文献类型：期刊论文
| 作者 | Xia, Ru1,5; Fu, Xinyue2,4; Ma, Shengzhou4; Xiao, Wenli3; Krishna Rao, M. V.1; Zhao, Peihao1; Wen, Liuqing2,4; Zhang, Jiabin1,2,4,5 |
| 刊名 | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
 |
| 出版日期 | 2025-09-12 |
| 页码 | 10 |
| ISSN号 | 0002-7863 |
| DOI | 10.1021/jacs.5c10568 |
| 通讯作者 | Wen, Liuqing(lwen@simm.ac.cn) ; Zhang, Jiabin(jiabinzhang@simm.ac.cn) |
| 英文摘要 | Glycosyl phosphosaccharides, a ubiquitous and crucial family of complex carbohydrates, widely occur in living organisms. Considering the importance in various physiological and pathophysiological processes, the synthesis of glycosyl phosphosaccharides is a key scientific issue in carbohydrate chemistry. However, their preparation presents two major challenges: achieving high stereoselectivity in phosphorylated glycosides and maintaining the stability of labile phosphoester linkages. Here, we redesigned the classical Koenigs-Knorr glycosylation reaction to efficiently synthesize 1,2-cis phosphorylated glycosides, using 1,7,13-trithio-18-crown-6 as a rationally designed additive. The key to this strategy is that the thiocrown ether could reverse the reaction mechanism from SN1 to SN2 pathways by modulating the interaction between silver and glycosyl chloride donors. This method enables phosphoryl glycosylation to proceed at room temperature without the use of acid or base. The feasibility of this strategy is demonstrated by the synthesis of 54 complex glycosyl phosphosaccharides with high efficiency and stereoselectivity, the gram-scale production of UDP-6-N3-Glc, and the synthesis of a tetrasaccharide diphosphate derived from Haemophilus influenzae type C. |
| WOS关键词 | CAPSULAR ANTIGEN ; PHOSPHATE ; ALPHA ; MONOESTERS ; RECEPTORS ; DIESTERS ; FRAGMENT |
| 资助项目 | National Natural Science Foundation of China[92478106] ; National Natural Science Foundation of China[2021A1515110588] ; Guangdong Basic and Applied Basic Research Foundation[XDB1060000] ; Strategic Priority Research Program of the Chinese Academy of Sciences[2024M753373] ; China Postdoctoral Science Foundation |
| WOS研究方向 | Chemistry |
| 语种 | 英语 |
| WOS记录号 | WOS:001570836800001 |
| 出版者 | AMER CHEMICAL SOC |
| 源URL | [http://119.78.100.183/handle/2S10ELR8/321465]  |
| 专题 | 中国科学院上海药物研究所 |
| 通讯作者 | Wen, Liuqing; Zhang, Jiabin |
| 作者单位 | 1.Chinese Acad Sci, Zhongshan Inst Drug Discovery, Shanghai Inst Mat Med, Zhongshan 528400, Guangdong, Peoples R China 2.Univ Chinese Acad Sci, Beijing 100049, Peoples R China 3.Southern Med Univ, Sch Pharmaceut Sci, Guangzhou 510515, Guangdong, Peoples R China 4.Chinese Acad Sci, Shanghai Inst Mat Med, Carbohydrate Based Drug Res Ctr, Shanghai 201203, Peoples R China 5.Guizhou Med Univ, Sch Pharmaceut Sci, Guiyang 561113, Guizhou, Peoples R China |
| 推荐引用方式 GB/T 7714 | Xia, Ru,Fu, Xinyue,Ma, Shengzhou,et al. Thiocrown Ether: Reversing SN1 to SN2 Pathways in 1,2-cis Phosphoryl Glycosylation[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2025:10. |
| APA | Xia, Ru.,Fu, Xinyue.,Ma, Shengzhou.,Xiao, Wenli.,Krishna Rao, M. V..,...&Zhang, Jiabin.(2025).Thiocrown Ether: Reversing SN1 to SN2 Pathways in 1,2-cis Phosphoryl Glycosylation.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,10. |
| MLA | Xia, Ru,et al."Thiocrown Ether: Reversing SN1 to SN2 Pathways in 1,2-cis Phosphoryl Glycosylation".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2025):10. |
入库方式： OAI收割
来源：上海药物研究所
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