Transition-Metal-Free β-Selective C-Glycosylation of β-Glycosyl Boronates via Stereoretentive 1,2-Migration

Yasutomi, Hiroki; Takeda, Daiki; Yoritate, Makoto; Higashibayashi, Shuhei; Sugai, Takeshi; Hirai, Go

doi:10.1055/a-1989-2541

Cited by 3 publications

(2 citation statements)

References 41 publications

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“…Oxidative addition to 11 and capture of 13 by the Ni complex should afford the Ni(III) complex 14 , and then reductive elimination selectively delivers the α-C-glycoside 12 , along with the Ni(I) complex, which can be reduced to Ni(0) by Ir(II). Despite recent reports on direct C -vinyl glycosylation, − our fluorovinyl C -glycosylation approach is distinct in that it provides access to three types of pseudo-glycans/glycoconjugates for biological evaluation.…”

Section: Results and Discussionmentioning

confidence: 99%

Linkage-Editing Pseudo-Glycans: A Reductive α-Fluorovinyl-C-Glycosylation Strategy to Create Glycan Analogs with Altered Biological Activities

Moriyama,

Yoritate,

Kato

et al. 2024

J. Am. Chem. Soc.

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The acetal (O-glycoside) bonds of glycans and glycoconjugates are chemically and biologically vulnerable, and therefore C-glycosides are of interest as more stable analogs. We hypothesized that, if the O-glycoside linkage plays a vital role in glycan function, the biological activities of C-glycoside analogs would vary depending on their substituents. Based on this idea, we adopted a "linkage-editing strategy" for the creation of glycan analogs (pseudo-glycans). We designed three types of pseudoglycans with CH 2 and CHF linkages, which resemble the Oglycoside linkage in terms of bond lengths, angles, and bulkiness, and synthesized them efficiently by means of fluorovinyl Cglycosylation and selective hydrogenation reactions. Application of this strategy to isomaltose (IM), an inducer of amylase expression, and α-GalCer, which activates iNKT cells, resulted in the discovery of CH 2 -IM, which shows increased amylase production ability, and CHF-α-GalCer, which shows activity opposite that of native α-GalCer, serving as an antagonist of iNKT cells.

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Section: Results and Discussionmentioning

confidence: 99%

Linkage-Editing Pseudo-Glycans: A Reductive α-Fluorovinyl-C-Glycosylation Strategy to Create Glycan Analogs with Altered Biological Activities

Moriyama,

Yoritate,

Kato

et al. 2024

J. Am. Chem. Soc.

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“…Subsequent cross-metathesis of the C-vinyl glycosides with vinylated glucose or galactose, and hydrogenation of the resulting internal C–C double bond finally afforded the CH 2 -linked 2-deoxy disaccharides (Scheme 18 ). 25…”

Section: Zweifel Olefination In Natural Product Synthesismentioning

confidence: 99%

Recent Progress on the Zweifel Olefination: An Update

Song,

2023

Synthesis

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During the past several decades, Zweifel olefination has emerged as one of the most powerful and reliable tools for constructing C–C double bonds. This reaction features high efficiency, good versatility, nonuse of transition metals, and perfect stereospecificity, which make it superior to many other olefination methods. Since the summary of Zweifel olefination’s 50-years history was published in 2017 by Aggarwal et al., remarkable achievements have been made in terms of employing new organometallic species, proceeding through electrochemical or photochemical pathways, and furnishing new kinds of products. This short review summarizes and discusses the very recent progress in Zweifel olefination and its latest application in natural products synthesis. 1 Introduction 2 Zweifel Olefination with New Organometallic Species 3 Zweifel Olefination with New Migrating Groups 4 Electrochemical and Photocatalyzed Zweifel Olefination 5 New Elimination and Migration Patterns of Zweifel Olefination 6 Zweifel Olefination in Natural Product Synthesis 7 Other Reactions Involving the Zweifel Olefination Mechanism 8 Conclusions and Outlook

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Linkage-Editing of Melibiosamine: Synthesis and Biological Evaluation of CH₂- and CHF-Linked Analogs

Moritsuka,

Kiya,

Moriyama

et al. 2024

J. Org. Chem.

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Melibiosamine (Gal-α(1,6)-GlcNH2), consisting of galactose and glucosamine linked by an α(1,6)-glycosidic bond, is an artificial disaccharide derivative that selectively inhibits the proliferation of K562 tumor cells relative to HUC-F2 normal cells. In this study, we employed a linkage-editing strategy to synthesize CH2- and CHF-linked melibiosamine analogs through chemo- and stereoselective hydrogenation of fluorovinyl-C-glycoside. (R)-CHF-Melibiosamine exhibited more potent antiproliferative activity than O-linked melibiosamine, while (S)-CHF-melibiosamine was less potent.

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Transition-Metal-Free β-Selective C-Glycosylation of β-Glycosyl Boronates via Stereoretentive 1,2-Migration

Cited by 3 publications

References 41 publications

Linkage-Editing Pseudo-Glycans: A Reductive α-Fluorovinyl-C-Glycosylation Strategy to Create Glycan Analogs with Altered Biological Activities

Linkage-Editing Pseudo-Glycans: A Reductive α-Fluorovinyl-C-Glycosylation Strategy to Create Glycan Analogs with Altered Biological Activities

Recent Progress on the Zweifel Olefination: An Update

Linkage-Editing of Melibiosamine: Synthesis and Biological Evaluation of CH₂- and CHF-Linked Analogs

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Transition-Metal-Free β-Selective C-Glycosylation of β-Glycosyl Boronates via Stereoretentive 1,2-Migration

Cited by 3 publications

References 41 publications

Linkage-Editing Pseudo-Glycans: A Reductive α-Fluorovinyl-C-Glycosylation Strategy to Create Glycan Analogs with Altered Biological Activities

Linkage-Editing Pseudo-Glycans: A Reductive α-Fluorovinyl-C-Glycosylation Strategy to Create Glycan Analogs with Altered Biological Activities

Recent Progress on the Zweifel Olefination: An Update

Linkage-Editing of Melibiosamine: Synthesis and Biological Evaluation of CH2- and CHF-Linked Analogs

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Linkage-Editing of Melibiosamine: Synthesis and Biological Evaluation of CH₂- and CHF-Linked Analogs