Cao Shen, Zhang Haobo, Chen Mingshuo, Zhu Niming, Zhan Beibei, Xu Peng, Chen Xiaoping, Yu Biao, Zhang Xiaheng
School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, 1 Sub-lane Xiangshan, Hangzhou, 310024, P. R. China.
State Key Laboratory of Chemical Biology, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.
Angew Chem Int Ed Engl. 2024 Dec 20;63(52):e202412436. doi: 10.1002/anie.202412436. Epub 2024 Oct 24.
The selective functionalization of carbohydrates holds a central position in synthetic carbohydrate chemistry, driving the ongoing quest for ideal approaches to manipulate these compounds. In this study, we introduce a general strategy that enables the regiodivergent functionalization of saccharides. The use of electron-deficient photoactive 4-tetrafluoropyridinylthio (SPyf) fragment as an adaptable activating group, facilitated efficient functionalization across all saccharide sites. More importantly, this activating group can be directly installed at the C1, C5 and C6 positions of biomass-derived carbohydrates in a single step and in a site-selective manner, allowing for the efficient and precision-oriented modification of unprotected saccharides and glycans.
碳水化合物的选择性官能团化在合成碳水化合物化学中占据核心地位，推动着人们不断探索理想的方法来操控这些化合物。在本研究中，我们引入了一种通用策略，该策略能够实现糖类的区域发散性官能团化。使用缺电子的光活性4-四氟吡啶硫基（SPyf）片段作为一种适应性强的活化基团，促进了在所有糖类位点上的高效官能团化。更重要的是，该活化基团可以一步且位点选择性地直接安装在生物质衍生碳水化合物的C1、C5和C6位置，从而实现对未保护的糖类和聚糖的高效且精准导向的修饰。
