Affiliation:
1. Institute of Pharmaceutical Science and Technology College of Chemistry Fuzhou University Fuzhou 350108 China
2. State Key Laboratory of Elemento‐organic Chemistry College of Chemistry Nankai University Weijin Road No. 94 Tianjin 300071 China
3. Haihe Laboratory of Sustainable Chemical Transformations Tianjin 300192 China
4. Key Laboratory of Organofluorine Chemistry Shanghai Institute of Organic Chemistry Chinese Academy of Sciences Shanghai 200032 China
Abstract
AbstractA 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.
Funder
National Natural Science Foundation of China
Fuzhou University
Fundamental Research Funds for the Central Universities
Subject
General Physics and Astronomy,General Engineering,Biochemistry, Genetics and Molecular Biology (miscellaneous),General Materials Science,General Chemical Engineering,Medicine (miscellaneous)