Visible-light-promoted direct desulfurization of glycosyl thiols to access C-glycosides
Abstract C-Glycosides are essential for the study of biological processes and the development of carbohydrate-based drugs. Despite the tremendous hurdles, glycochemists have often fantasized about the efficient, highly stereoselective synthesis of C-glycosides with the shortest steps under mild cond...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2024-10-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-53563-0 |
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| author | Demeng Xie Wei Zeng Jian Yang Xiaofeng Ma |
| author_facet | Demeng Xie Wei Zeng Jian Yang Xiaofeng Ma |
| author_sort | Demeng Xie |
| collection | DOAJ |
| description | Abstract C-Glycosides are essential for the study of biological processes and the development of carbohydrate-based drugs. Despite the tremendous hurdles, glycochemists have often fantasized about the efficient, highly stereoselective synthesis of C-glycosides with the shortest steps under mild conditions. Herein, we report a desulfurative radical protocol to synthesize C-alkyl glycosides and coumarin C-glycosides under visible-light induced conditions without the need of an extra photocatalyst, in which stable and readily available glycosyl thiols that could be readily obtained from native sugars are activated in situ by pentafluoropyridine. The benefits of this procedure include high stereoselectivity, broad substrate scope, and easy handling. Mechanistic studies indicate that the in situ produced tetrafluoropyridyl S-glycosides form key electron donor–acceptor (EDA) complexes with Hantzsch ester (for C-alkyl glycosides) or Et3N (for coumarin C-glycosides), which, upon irradiation with visible light, trigger a cascade of glycosyl radical processes to access C-glycosides smoothly. |
| format | Article |
| id | doaj-art-a648cbc5e8ee453599076151d4c4190e |
| institution | OA Journals |
| issn | 2041-1723 |
| language | English |
| publishDate | 2024-10-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-a648cbc5e8ee453599076151d4c4190e2025-08-20T02:11:22ZengNature PortfolioNature Communications2041-17232024-10-0115111010.1038/s41467-024-53563-0Visible-light-promoted direct desulfurization of glycosyl thiols to access C-glycosidesDemeng Xie0Wei Zeng1Jian Yang2Xiaofeng Ma3Natural Products Research Center, Chengdu Institute of Biology, Chinese Academy of SciencesNatural Products Research Center, Chengdu Institute of Biology, Chinese Academy of SciencesNatural Products Research Center, Chengdu Institute of Biology, Chinese Academy of SciencesNatural Products Research Center, Chengdu Institute of Biology, Chinese Academy of SciencesAbstract C-Glycosides are essential for the study of biological processes and the development of carbohydrate-based drugs. Despite the tremendous hurdles, glycochemists have often fantasized about the efficient, highly stereoselective synthesis of C-glycosides with the shortest steps under mild conditions. Herein, we report a desulfurative radical protocol to synthesize C-alkyl glycosides and coumarin C-glycosides under visible-light induced conditions without the need of an extra photocatalyst, in which stable and readily available glycosyl thiols that could be readily obtained from native sugars are activated in situ by pentafluoropyridine. The benefits of this procedure include high stereoselectivity, broad substrate scope, and easy handling. Mechanistic studies indicate that the in situ produced tetrafluoropyridyl S-glycosides form key electron donor–acceptor (EDA) complexes with Hantzsch ester (for C-alkyl glycosides) or Et3N (for coumarin C-glycosides), which, upon irradiation with visible light, trigger a cascade of glycosyl radical processes to access C-glycosides smoothly.https://doi.org/10.1038/s41467-024-53563-0 |
| spellingShingle | Demeng Xie Wei Zeng Jian Yang Xiaofeng Ma Visible-light-promoted direct desulfurization of glycosyl thiols to access C-glycosides Nature Communications |
| title | Visible-light-promoted direct desulfurization of glycosyl thiols to access C-glycosides |
| title_full | Visible-light-promoted direct desulfurization of glycosyl thiols to access C-glycosides |
| title_fullStr | Visible-light-promoted direct desulfurization of glycosyl thiols to access C-glycosides |
| title_full_unstemmed | Visible-light-promoted direct desulfurization of glycosyl thiols to access C-glycosides |
| title_short | Visible-light-promoted direct desulfurization of glycosyl thiols to access C-glycosides |
| title_sort | visible light promoted direct desulfurization of glycosyl thiols to access c glycosides |
| url | https://doi.org/10.1038/s41467-024-53563-0 |
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