Anion‐Bridged Dual Hydrogen Bond Enabled Concerted Addition of Phenol to Glycal
Abstract 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 intera...
| Main Authors: | , , , , , , , |
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| Format: | Article |
| Language: | English |
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Wiley
2024-03-01
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| Series: | Advanced Science |
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| Online Access: | https://doi.org/10.1002/advs.202308513 |
| _version_ | 1797255025175560192 |
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| author | Qinbo Jiao Zhenbo Guo Mingwen Zheng Wentao Lin Yujie Liao Weitao Yan Tianfei Liu Chunfa Xu |
| author_facet | Qinbo Jiao Zhenbo Guo Mingwen Zheng Wentao Lin Yujie Liao Weitao Yan Tianfei Liu Chunfa Xu |
| author_sort | Qinbo Jiao |
| collection | DOAJ |
| description | Abstract 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. |
| first_indexed | 2024-04-24T21:59:17Z |
| format | Article |
| id | doaj.art-b26e868b3fae4fbfa3c4a9597de0e755 |
| institution | Directory Open Access Journal |
| issn | 2198-3844 |
| language | English |
| last_indexed | 2024-04-24T21:59:17Z |
| publishDate | 2024-03-01 |
| publisher | Wiley |
| record_format | Article |
| series | Advanced Science |
| spelling | doaj.art-b26e868b3fae4fbfa3c4a9597de0e7552024-03-20T12:56:12ZengWileyAdvanced Science2198-38442024-03-011111n/an/a10.1002/advs.202308513Anion‐Bridged Dual Hydrogen Bond Enabled Concerted Addition of Phenol to GlycalQinbo Jiao0Zhenbo Guo1Mingwen Zheng2Wentao Lin3Yujie Liao4Weitao Yan5Tianfei Liu6Chunfa Xu7Institute of Pharmaceutical Science and Technology College of Chemistry Fuzhou University Fuzhou 350108 ChinaState Key Laboratory of Elemento‐organic Chemistry College of Chemistry Nankai University Weijin Road No. 94 Tianjin 300071 ChinaInstitute of Pharmaceutical Science and Technology College of Chemistry Fuzhou University Fuzhou 350108 ChinaInstitute of Pharmaceutical Science and Technology College of Chemistry Fuzhou University Fuzhou 350108 ChinaInstitute of Pharmaceutical Science and Technology College of Chemistry Fuzhou University Fuzhou 350108 ChinaInstitute of Pharmaceutical Science and Technology College of Chemistry Fuzhou University Fuzhou 350108 ChinaState Key Laboratory of Elemento‐organic Chemistry College of Chemistry Nankai University Weijin Road No. 94 Tianjin 300071 ChinaInstitute of Pharmaceutical Science and Technology College of Chemistry Fuzhou University Fuzhou 350108 ChinaAbstract 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.https://doi.org/10.1002/advs.202308513concerted additionglycosylationhydrogen bondorganocatalysisphenolic glycoside |
| spellingShingle | Qinbo Jiao Zhenbo Guo Mingwen Zheng Wentao Lin Yujie Liao Weitao Yan Tianfei Liu Chunfa Xu Anion‐Bridged Dual Hydrogen Bond Enabled Concerted Addition of Phenol to Glycal Advanced Science concerted addition glycosylation hydrogen bond organocatalysis phenolic glycoside |
| title | Anion‐Bridged Dual Hydrogen Bond Enabled Concerted Addition of Phenol to Glycal |
| title_full | Anion‐Bridged Dual Hydrogen Bond Enabled Concerted Addition of Phenol to Glycal |
| title_fullStr | Anion‐Bridged Dual Hydrogen Bond Enabled Concerted Addition of Phenol to Glycal |
| title_full_unstemmed | Anion‐Bridged Dual Hydrogen Bond Enabled Concerted Addition of Phenol to Glycal |
| title_short | Anion‐Bridged Dual Hydrogen Bond Enabled Concerted Addition of Phenol to Glycal |
| title_sort | anion bridged dual hydrogen bond enabled concerted addition of phenol to glycal |
| topic | concerted addition glycosylation hydrogen bond organocatalysis phenolic glycoside |
| url | https://doi.org/10.1002/advs.202308513 |
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