2023 Fiscal Year Final Research Report
Development of a new method for generating glycosyl radical and application to C-glycosylation
| Project/Area Number |
22K14683
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| Research Category |
Grant-in-Aid for Early-Career Scientists
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| Allocation Type | Multi-year Fund |
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| Review Section |
Basic Section 33020:Synthetic organic chemistry-related
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| Research Institution | Kyushu University |
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Principal Investigator |
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| Project Period (FY) |
2022-04-01 – 2024-03-31
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| Keywords | 擬糖鎖 / C-グリコシド / 光触媒 / 無保護 / グリコシルラジカル / ラジカル |
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| Outline of Final Research Achievements |
While native glycans consist of enzymatically cleavable O-glycosidic linkage, C-glycoside analogs exhibit glycosyl hydrolase resistance, thus capturing attention from researchers in glycoscience and chemical biology. Nevertheless, their synthesis has required the protection of the sugar hydroxyl groups and the aglycone, making direct C-glycosylation with water-soluble biomacromolecules challenging. In response to this challenge, we have developed an innovative C-glycosylation strategy utilizing unprotected glycosyl sulfinate, notable for its high water solubility, as a novel sugar donor. Upon photo-irradiation of a solution of glycosyl sulfinate and photocatalyst, unprotected glycosyl radicals were formed. Subsequent Giese radical addition to a Michael acceptor facilitated the successful direct synthesis of unprotected C-glycosides.
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| Free Research Field |
有機合成化学
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| Academic Significance and Societal Importance of the Research Achievements |
本研究では、これまでに困難であった無保護C-グリコシドの直接合成法を開発した。新たに見出した無保護グリコシルスルフィネートは、安価な原料と試薬から大量合成することが可能であり、室温下極めて安定な固体である。水溶性が極めて高く、水や緩衝溶液に容易に溶解し、水溶性アグリコンと直接反応させることが可能である。これまでに、無保護アクリル酸やN-アセチルデヒドロアラニンとの直接C-グリコシル化に成功した。本結果は、翻訳後修飾により生じたデヒドロアラニンを有するたんぱく質などと直接連結できる可能性を示唆している。
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