Jiao Qinbo, Guo Zhenbo, Zheng Mingwen, Lin Wentao, Liao Yujie, Yan Weitao, Liu Tianfei, Xu Chunfa
Institute of Pharmaceutical Science and Technology, College of Chemistry, Fuzhou University, Fuzhou, 350108, China.
State Key Laboratory of Elemento-organic Chemistry, College of Chemistry, Nankai University, Weijin Road No. 94, Tianjin, 300071, China.
Adv Sci (Weinh). 2024 Mar;11(11):e2308513. doi: 10.1002/advs.202308513. Epub 2024 Jan 15.
A noncovalent organocatalytic concerted addition of phenol to glycal is developed for the stereoselective and regioselective construction of biologically important phenolic 2-deoxyglycosides, featuring wide substrate tolerance. The method relies on an anion-bridged dual hydrogen bond interaction which is experimentally proved by Nuclear Magnetic Resonance (NMR), Ultraviolet and visible (UV-vis), and fluorescence analysis. Experimental evidence including kinetic analysis, Kinetic Isotope Effect (KIE) studies, linear free energy relationship, Hammett plot, and density functional theory (DFT) calculations is provided for a concerted mechanism where a high-energy oxocarbenium ion is not formed. In addition, the potential utility of this method is further demonstrated by the synthesis of biologically active glycosylated flavones. The benchmarking studies demonstrate significant advances in this newly developed method compared to previous approaches.
开发了一种非共价有机催化的苯酚对糖烯的协同加成反应，用于立体选择性和区域选择性构建具有生物学重要性的酚基2-脱氧糖苷，该方法具有广泛的底物耐受性。该方法依赖于阴离子桥连的双氢键相互作用，核磁共振（NMR）、紫外可见（UV-vis）和荧光分析实验证明了这一点。提供了包括动力学分析、动力学同位素效应（KIE）研究、线性自由能关系、哈米特图和密度泛函理论（DFT）计算在内的实验证据，以支持不形成高能氧鎓离子的协同机理。此外，通过合成具有生物活性的糖基化黄酮进一步证明了该方法的潜在实用性。基准研究表明，与以前的方法相比，这种新开发的方法有了显著进展。
