التفاصيل البيبلوغرافية
| العنوان: |
Site‐ and Stereoselective Glycomodification of Biomolecules through Carbohydrate‐Promoted Pictet–Spengler Reaction. |
| المؤلفون: |
Liu, Bo, Zou, Xiangman, Zhang, Yue, Yang, Yang, Xu, Hao, Tang, Feng, Yu, Huixin, Xia, Fei, Liu, Zhi, Zhao, Jianwei, Shi, Wei, Huang, Wei |
| المصدر: |
Angewandte Chemie International Edition; Apr2024, Vol. 63 Issue 16, p1-10, 10p |
| مصطلحات موضوعية: |
PICTET-Spengler reaction, BIOMOLECULES, N-terminal residues, CARBOHYDRATES, GLYCOPEPTIDES, GLYCOCONJUGATES, GLYCANS |
| مستخلص: |
Carbohydrates play pivotal roles in an array of essential biological processes and are consequently involved in many diseases. To meet the needs of glycobiology research, chemical enzymatic and non‐enzymatic methods have been developed to generate glycoconjugates with well‐defined structures. Herein, harnessing the unique properties of C6‐oxidized glycans, we report a straightforward and robust strategy for site‐ and stereoselective glycomodification of biomolecules with N‐terminal tryptophan residues by a carbohydrate‐promoted Pictet–Spengler reaction, which is not adapted to typical aldehyde substrates under biocompatible conditions. This method reliably delivers highly homogeneous glycoconjugates with stable linkages and thus has great potential for functional modulation of peptides and proteins in glycobiology research. Moreover, this reaction can be performed at the glycosites of glycopeptides, glycoproteins and living‐cell surfaces in a site‐specific manner. Control experiments indicated that the protected α‐O atom of aldehyde donors and free N−H bond of the tryptamine motif are crucial for this reaction. Mechanistic investigations demonstrated that the reaction exhibited a first‐order dependence on both tryptophan and glycan, and deprotonation/rearomatization of the pentahydro‐β‐carbolinium ion intermediate might be the rate‐determining step. [ABSTRACT FROM AUTHOR] |
|
Copyright of Angewandte Chemie International Edition is the property of Wiley-Blackwell and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) |
| قاعدة البيانات: |
Complementary Index |
Full Text Finder