Radical Pathway Glycosylation Empowered by Bench-Stable Glycosyl Donors

Accounts of Chemical Research, Год журнала: 2023, Номер 56(18), С. 2473 - 2488

Опубликована: Авг. 18, 2023

ConspectusThe study of carbohydrates has emerged as a crucial research area in various disciplines due to their pivotal roles cellular processes. To facilitate in-depth exploration biological functions, chemical glycosylation reactions that allow facile access glycoconjugates broad community are highly needed. In classical reactions, glycosyl donor is activated by an acid generate reactive electrophilic intermediate, which subsequently forms glycosidic bond upon reaction with nucleophilic acceptor. Such ionic pathway been the mainstay technique for glycoconjugate synthesis and allowed numerous intricate structures. Nevertheless, limitations still exist. For instance, when labile donors or harsh activating conditions required, these methods show limited tolerance hydroxyl groups abundant on sugar rings. addition, achieving good stereocontrol represents another longstanding obstacle. recent years, new modes activation have sought tackle above challenges.We noted passing through intermediacy radicals via cascade single-electron transfer steps possess significant but underexplored potential. Progress this slow large part dearth handy maneuver radicals. Most existing call either forcing unstable/inconvenient starting materials. order better exploit power radical glycosylation, we developed range donors─namely, sulfoxides, sulfones, sulfinates─that bench stable can be readily prepared from simple These form under mild conditions. Enabled use donors, series could used making O-, S-, C-glycosides, some were previously difficult access. many cases, no protecting group required. As illustration potential utility, our adopted preparation sugar–drug conjugates, sugar–DNA glycopeptides, even glycoproteins. While most cases intrinsic reactivity intermediates explored axially configured products, also utilization external, delicate reagents, catalysts override such innate preference achieve catalyst-controlled stereoselectivity.We believe enormous inspire development novel glycoside synthesis. Account, highlight design principles summarize advancements enabled use, provide outlook future directions field.

Язык: Английский

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Transformations of carbohydrate derivatives enabled by photocatalysis and visible light photochemistry

Chemical Science, Год журнала: 2024, Номер 15(4), С. 1204 - 1236

Опубликована: Янв. 1, 2024

This review article highlights the diverse ways in which recent developments areas of photocatalysis and visible light photochemistry are impacting synthetic carbohydrate chemistry.

Язык: Английский

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Direct Formation of Amide-Linked C-Glycosyl Amino Acids and Peptides via Photoredox/Nickel Dual Catalysis

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(8), С. 5502 - 5510

Опубликована: Фев. 15, 2024

Glycoproteins account for numerous biological processes including those associated with diseases and infections. The advancement of glycopeptides has emerged as a promising strategy unraveling pathways discovering novel medicines. In this arena, key challenge arises from the absence efficient synthetic strategies to access glycoproteins. Here, we present highly concise approach bridging saccharides amino acids peptides through an amide linkage. Our amide-linked C-glycosyl are synthesized cooperative Ni-catalyzed photoredox processes. catalytic process generates glycosyl radical carbonyl radical, which subsequently combine yield products. saccharide reaction partners encompass mono-, di-, trisaccharides. All 20 natural acids, peptides, their derivatives can efficiently undergo glycosylations yields ranging acceptable high, demonstrating excellent stereoselectivities. As substantial expansion applications, have shown that simple function versatile building units constructing C-glycopeptides intricate spatial complexities.

Язык: Английский

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Photoredox-catalyzed protecting-group-free C-glycosylation with glycosyl sulfinate via the Giese reaction

Chemical Communications, Год журнала: 2023, Номер 59(55), С. 8564 - 8567

Опубликована: Янв. 1, 2023

C-Glycoside analogs of naturally occurring glycoconjugates are useful tools for chemical biology studies, but their synthesis usually requires protection the hydroxyl groups glycosyl donors. Here we report protecting-group-free and photoredox-catalyzed C-glycosylation with sulfinates Michael acceptors via Giese radical addition.

Язык: Английский

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Diverse Synthesis of C-Glycosides by Stereoselective Ni-Catalyzed Carboboration of Glycals

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(28), С. 18866 - 18872

Опубликована: Июль 5, 2024

C-Glycosides are important structures that common to natural products and pharmaceutical agents. Established methods for their synthesis involve the reaction of an activated anomeric carbon. In this study, we report a conceptually new approach involves stereoselective Ni-catalyzed carboboration glycals. these reactions, not only is C–C bond formed at carbon, but synthetically useful C–B also installed. Upon oxidation, differentially protected C-glycosides be formed. addition, stereospecific manipulation leads diverse C-glycosides. Finally, application method in established C-glycosides, such as C-glycosyl amino acids, well strategy make all possible diastereomers C1 C2.

Язык: Английский

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Palladium-catalyzed Suzuki-Miyaura cross-couplings of stable glycal boronates for robust synthesis of C-1 glycals

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июнь 19, 2024

Abstract C- 1 Glycals serve as pivotal intermediates in synthesizing diverse C -glycosyl compounds and natural products, necessitating the development of concise, efficient user-friendly methods to obtain glycosides is essential. The Suzuki-Miyaura cross-coupling glycal boronates notable for its reliability non-toxic nature, but donor stability remains a challenge. Herein, we achieve significant breakthrough by developing stable boronates, effectively overcoming issue glycal-based Suzuki–Miyaura coupling. Leveraging balanced reactivity our establish robust palladium-catalyzed reaction, facilitating formation various C( sp 2 )-C( ), 3 ) bonds under mild conditions. Notably, expand upon this achievement DNA-compatible reaction synthesize glycal-DNA conjugates. With excellent reactivity, stability, generality, ease handling, method holds promise widespread appication preparation products.

Язык: Английский

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Recent Advances in Organic Photocatalyst‐Promoted Carbohydrate Synthesis and Modification under Light Irradiation

Chemistry - An Asian Journal, Год журнала: 2025, Номер unknown

Опубликована: Янв. 2, 2025

Abstract Photoredox catalysis has been developed as a sustainable and eco‐friendly catalytic strategy, which might provide innovative solutions to solve the current synthetic challenges barriers in carbohydrate chemistry. During last few decades, study of organic photocatalyst‐promoted synthesis modification received significant attention, provides an excellent inexpensive metal‐free alternative photoredox well introduces new fastest‐growing era access complex carbohydrates simply. In this review, we aim overview under light irradiation, is expected directions for further investigation.

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

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(17), С. 11909 - 11920

Опубликована: Авг. 9, 2024

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

Язык: Английский

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Exploration of Glycosyl Dithioimidocarbonates in Photoinduced Desulfurative Cross-Coupling Reactions

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Сен. 30, 2024

Readily synthesized bench-stable glycosyl dithioimidocarbonates are useful

Язык: Английский

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