通过催化 TfOH 活化供体-受体环氧乙烷实现硫代糖苷和硒代糖苷的菌株释放糖基化反应

IF 5 1区化学 Q1 CHEMISTRY, ORGANIC Organic Letters Pub Date : 2025-04-22 DOI:10.1021/acs.orglett.5c01191

Xin-Yu Fang, Xing-Le Liu, Jia-Ying Shen, Long-Xuan Zhao, Xiong Xiao

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引用次数: 0

摘要

我们开发了一种在环境条件下利用供体-受体氧环烷（DAOs）和三酸（2 mol %）通过C-C键裂解制备硫代/硒代糖苷的菌株释放糖基化方法。该方案是有效的酸敏感和立体受阻底物，显示出广泛的适用性。实验结果和DFT计算表明，DAO/ tfoh衍生的两性离子氧羰基通过糖基两性离子中间体激活供体，促进糖苷键的形成和质子转移。该方法开创了环氧化物介导的硫代/硒代糖苷活化，为多种糖苷合成提供了温和、高效的平台，并推动了碳水化合物化学方法的发展。

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Strain-Release Glycosylation of Thio- and Selenoglycosides Enabled by Activation of Donor–Acceptor Oxiranes with Catalytic TfOH

We have developed a strain-release glycosylation method for thio/selenoglycosides utilizing donor–acceptor oxiranes (DAOs) and triflic acid (2 mol %) via C–C bond cleavage under ambient conditions. This protocol is effective for acid-sensitive and sterically hindered substrates, demonstrating broad applicability. Experimental results and DFT calculations reveal that DAO/TfOH-derived zwitterionic oxocarbenium species activate donors via glycosyl zwitterion intermediates, facilitating glycosidic bond formation and proton transfer. This approach pioneers epoxide-mediated thio/selenoglycosides activation, offering a mild, efficient platform for diverse glycoside synthesis and advancing methodologies in carbohydrate chemistry.

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来源期刊

Organic Letters 化学-有机化学

CiteScore

9.30

自引率

11.50%

发文量

1607

审稿时长

1.5 months

期刊介绍： Organic Letters invites original reports of fundamental research in all branches of the theory and practice of organic, physical organic, organometallic,medicinal, and bioorganic chemistry. Organic Letters provides rapid disclosure of the key elements of significant studies that are of interest to a large portion of the organic community. In selecting manuscripts for publication, the Editors place emphasis on the originality, quality and wide interest of the work. Authors should provide enough background information to place the new disclosure in context and to justify the rapid publication format. Back-to-back Letters will be considered. Full details should be reserved for an Article, which should appear in due course.