Liu Ying-Guo, Zhong Zetao, Tang Yuyang, Wang Hongling, Vummaleti Sai Vikrama Chaitanya, Peng Xi, Peng Peng, Zhang Xinglong, Chi Yonggui Robin
Division of Molecular Catalysis and Synthesis, Henan Institute of Advanced Technology, Zhengzhou University, Zhengzhou, 450001, PR China.
Pingyuan laboratory, Zhengzhou University, Zhengzhou, 450001, PR China.
Nat Commun. 2025 Jan 2;16(1):54. doi: 10.1038/s41467-024-55282-y.
Acylation stands as a fundamental process in both biological pathways and synthetic chemical reactions, with acylated saccharides and their derivatives holding diverse applications ranging from bioactive agents to synthetic building blocks. A longstanding objective in organic synthesis has been the site-selective acylation of saccharides without extensive pre-protection of alcohol units. In this study, we demonstrate that by simply altering the chirality of N-heterocyclic carbene (NHC) organic catalysts, the site-selectivity of saccharide acylation reactions can be effectively modulated. Our investigation reveals that this intriguing selectivity shift stems from a combination of factors, including chirality match/mismatch and inter- / intramolecular hydrogen bonding between the NHC catalyst and saccharide substrates. These findings provide valuable insights into catalyst design and reaction engineering, highlighting potential applications in glycoside analysis, such as fluorescent labelling, α/β identification, orthogonal reactions, and selective late-stage modifications.
酰化作用在生物途径和合成化学反应中都是一个基本过程，酰化糖类及其衍生物有着从生物活性剂到合成砌块等多种应用。有机合成中的一个长期目标是在不大量预先保护醇单元的情况下对糖类进行位点选择性酰化。在本研究中，我们证明，通过简单改变N-杂环卡宾（NHC）有机催化剂的手性，糖类酰化反应的位点选择性可以得到有效调控。我们的研究表明，这种有趣的选择性转变源于多种因素的组合，包括手性匹配/不匹配以及NHC催化剂与糖类底物之间的分子间/分子内氢键。这些发现为催化剂设计和反应工程提供了有价值的见解，突出了在糖苷分析中的潜在应用，如荧光标记、α/β鉴定、正交反应和选择性后期修饰。
