N-glycoside synthesis through combined copper- and photoredox-catalysed N-glycosylation of N-nucleophiles

Nature Synthesis, Год журнала: 2024, Номер 3(5), С. 623 - 632

Опубликована: Март 1, 2024

Язык: Английский

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Polarity-Matched Initiation of Radical-Polar Crossover Reactions for the Synthesis of C-Allyl Glycosides with gem-Difluoroalkene Groups

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(14), С. 10175 - 10179

Опубликована: Июль 8, 2024

Herein, we disclose a general method for the assembly of

Язык: Английский

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Nitrene-mediated glycosylation with thioglycoside donors under metal catalysis

Science Advances, Год журнала: 2025, Номер 11(8)

Опубликована: Фев. 21, 2025

Glycosylation chemistry plays a pivotal role in glycoscience. Recent substantial developments have poised the field to address emerging challenges related sustainability, cost efficiency, and robust applicability complex substrate settings. The transition from stoichiometric activation metal-catalyzed methods promises enhanced chemoselectivity greater precision controlling glycosidic bond breakage formation, key overcoming existing obstacles. Here, we report nitrene-mediated glycosylation strategy using regular aryl sulfide glycosyl donors easily accessible 3-methyl dioxazolone as an activator under catalysis of iron or ruthenium. iron-catalyzed system demonstrates exceptional catalytic reactivity, requiring little 0.1 mole % catalyst at room temperature, works well for peptide substrates. ruthenium-catalyzed can accommodate acid-sensitive functional groups challenging low-reactivity acceptors. Mechanistic investigations unveiled unusual multistep pathways involving sulfur imidation via nitrene transfer sulfur-to-oxygen rearrangement N-acyl sulfilimines donors.

Язык: Английский

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Tetrafluoropyridin-4-yl thioglycosides (TFPTGs): Versatile donors in C-, O-, and N-glycosidic construction

Tetrahedron Letters, Год журнала: 2025, Номер 160, С. 155563 - 155563

Опубликована: Март 31, 2025

Язык: Английский

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Minimally Protected and Stereoselective O-Glycosylation of Carboxylic Acid Allows Rapid Access to α-1-O- and 2-O-Acyl Glycosides

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 31, 2025

We herein reported a catalytic, minimally protected, and highly α-stereoselective glycosylation protocol using carboxylic acid as an acceptor glycosyl 8-alkynyl-1-naphthoate donor, enabling efficient access to unprotected α-1-O- 2-O-acyl glycosides. This method demonstrates excellent functional compatibility scope generality, allowing for the of wide range complex acids. Notably, we successfully synthesized two natural products, α-penta-O-galloyl-d-glucopyranose nyctanthesin A, this protocol. Mechanistic studies highlighted crucial role 1-O ester functionality in ensuring chemoselectivity important contribution 2-O facilitating reaction.

Язык: Английский

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Emerging Advances of the Radical Pathway Glycosylation Enabled by Bench‐Stable Glycosyl Donors: Glycosyl Sulfoxides, Glycosyl Sulfones, and Glycosyl Sulfinates

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(19), С. 4017 - 4041

Опубликована: Июль 30, 2024

Abstract In synthetic carbohydrate chemistry, the modification of glycosyl radicals pathway stands as a central area focus. The radical‐based reactions often demonstrate remarkable compatibility with various functional groups owing to mild initiation conditions. particular, identification novel radical precursors, combined advanced reaction techniques, has substantially broadened scope compound synthesis. Despite presence versatile donors, synthesis noble donors is still addressed need and challenges associated sugar chemistry. Currently, new class precursors been developed which enables production C ‐, S O N ‐glycosides efficiently. this light, we highlight strategies towards bench‐stable sulfoxides, sulphone, sulfite that can enable site‐, regio‐ stereoselective transformation protected or naked synthons in Here, review article covers recent developments selective diversification such alkylation, arylation, alkenylation, sulfuration, C−H activation, DNA conjugation via along mechanistic aspects, challenges, future directions.

Язык: Английский

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C–OH Bond Activation for Stereoselective Radical C-Glycosylation of Native Saccharides

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(47), С. 32269 - 32275

Опубликована: Ноя. 15, 2024

Radical C-glycosylation presents a flexible and efficient method for synthesizing C-glycosides. Existing methods always require multistep processes generating anomeric radicals. In this study, we introduce streamlined approach to produce radicals through direct C-OH bond homolysis of unmodified saccharides, eliminating the need protection, deprotection, or activation steps. These selectively couple with activated alkenes, yielding products high stereoselectivity (>20:1). This is applicable variety native monosaccharides, such as l-arabinose, d-arabinose, d-xylose, l-xylose, d-galactose, β-d-glucose, α-d-glucose, l-ribose, well oligosaccharides including α-lactose, d-(+)-melibiose, acarbose. We also extend amino acid peptide derivatives, demonstrate synthesis an anti-inflammatory agent.

Язык: Английский

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Stereoselective synthesis of α-glycosyl azides: allyl glycosyl sulfones as radical precursors

Chemical Communications, Год журнала: 2024, Номер 60(49), С. 6288 - 6291

Опубликована: Янв. 1, 2024

We introduce a radical reaction for the stereoselective synthesis of α-glycosyl azides using bench-stable allyl glycosyl sulfones as donor.

Язык: Английский

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A Radical Activation Strategy for Versatile and Stereoselective N‐Glycosylation

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(36)

Опубликована: Июнь 5, 2024

Previous N-glycosylation approaches have predominately involved acidic conditions, facing challenges of low stereoselectivity and limited scope. Herein, we introduce a radical activation strategy that enables versatile stereoselective using readily accessible glycosyl sulfinate donors under basic conditions exhibits exceptional tolerance towards various N-aglycones containing alkyl, aryl, heteroaryl nucleobase functionalities. Preliminary mechanistic studies indicate pivotal role iodide, which orchestrates the formation from subsequent generation key intermediate, configurationally well-defined is subsequently attacked by an N-aglycone in stereospecific S

Язык: Английский

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A Radical Activation Strategy for Versatile and Stereoselective N‐Glycosylation

Angewandte Chemie, Год журнала: 2024, Номер 136(36)

Опубликована: Июнь 5, 2024

Abstract Previous N‐glycosylation approaches have predominately involved acidic conditions, facing challenges of low stereoselectivity and limited scope. Herein, we introduce a radical activation strategy that enables versatile stereoselective using readily accessible glycosyl sulfinate donors under basic conditions exhibits exceptional tolerance towards various N‐aglycones containing alkyl, aryl, heteroaryl nucleobase functionalities. Preliminary mechanistic studies indicate pivotal role iodide, which orchestrates the formation from subsequent generation key intermediate, configurationally well‐defined is subsequently attacked by an N‐aglycone in stereospecific S N 2 manner to give desired N‐glycosides. An alternative route involving coupling nitrogen‐centered also proposed, affording exclusive 1,2‐ trans product. This novel approach promises broaden synthetic landscape N‐glycosides, offering powerful tool for construction complex glycosidic structures mild conditions.

Язык: Английский

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