Diversification of Glycosyl Compounds via Glycosyl Radicals

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(38)

Published: June 7, 2023

Glycosyl radical functionalization is one of the central topics in synthetic carbohydrate chemistry. Recent advances metal-catalyzed cross-coupling chemistry and metallaphotoredox catalysis provided powerful platforms for glycosyl diversification. In particular, discovery new precursors conjunction with these advanced reaction technologies have significantly expanded space compound synthesis. this Review, we highlight most recent progress area starting from 2021, reports included will be categorized based on different types better clarity.

Language: Английский

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Transformations of carbohydrate derivatives enabled by photocatalysis and visible light photochemistry

Chemical Science, Journal Year: 2024, Volume and Issue: 15(4), P. 1204 - 1236

Published: Jan. 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.

Language: Английский

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Recent advances on synthesis of C-glycosides

Carbohydrate Research, Journal Year: 2023, Volume and Issue: 530, P. 108856 - 108856

Published: June 5, 2023

Language: Английский

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

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(55), P. 8564 - 8567

Published: Jan. 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.

Language: Английский

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

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(3), P. 2237 - 2247

Published: Jan. 10, 2024

The acetal (O-glycoside) bonds of glycans and glycoconjugates are chemically biologically vulnerable, therefore C-glycosides interest as more stable analogs. We hypothesized that, if the O-glycoside linkage plays a vital role in glycan function, biological activities C-glycoside analogs would vary depending on their substituents. Based this idea, we adopted "linkage-editing strategy" for creation (pseudo-glycans). designed three types pseudo-glycans with CH2 CHF linkages, which resemble terms bond lengths, angles, bulkiness, synthesized them efficiently by means fluorovinyl C-glycosylation selective hydrogenation reactions. Application strategy to isomaltose (IM), an inducer amylase expression, α-GalCer, activates iNKT cells, resulted discovery CH2-IM, shows increased production ability, CHF-α-GalCer, activity opposite that native serving antagonist cells.

Language: Английский

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Recent Advances and Strategies towards Synthesis of Indolyl and Tryptophan‐C‐Glycoside Scaffolds

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(7), P. 1484 - 1508

Published: Feb. 29, 2024

Abstract Recently, C ‐glycosidic bonds have emerged as pivotal elementary units present in many naturally occurring alkaloids well pharmaceutically active molecules. Because of the stability and great utility ‐glycosides, synthetic approaches en route to C−C bond formation gradually become a center attraction carbohydrate chemistry. Towards these researches, ‐glycosylation with heteroaryl moieties like indole, tryptophan can remarkably expand functional structural evolution, which has value for medicinal chemists chemical biologists. The indolyl tryptophan‐ ‐glycosides unique structures biological activities that attracted number studies. Therefore, motifs possessed an extensive interest direction efficient synthesis. Herein, this review systematically summarizes classical ‐heteroaryl glycosides mainly focusing on indole Furthermore, highlighted recently developed metal‐catalyzed C−H functionalization photoinduced cross‐coupling strategies aim control regioselectivity diastereoselectivity reaction In view type, mechanism, status, will cover synthesis diverse regio‐ from four perspectives include a) conventional approach, b) heterocyclization sequence, c) functionalization, d) cross‐coupling. 1. Introduction 2. Strategies 2.1. Conventional approach 2.2. Heterocyclization sequence 2.3. Metal‐catalyzed 2.4. Photoinduced 3. Summary Outlook

Language: Английский

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Modulable Photocatalyzed Strategies for the Synthesis of α-C-Glycosyl Alanine Analogues via the Giese Reaction with Dehydroalanine Derivates

Organic Letters, Journal Year: 2023, Volume and Issue: 25(26), P. 4862 - 4867

Published: June 22, 2023

Herein, we present the α-selective Giese reaction between pyranosyl/furanosyl bromides and dehydroalanine analogues, which provides access to a library of highly valuable α-C-glycosyl alanines. The key C-glycosyl radical is generated through photocatalysis by either new generation copper(I) complex [(DPEPhos)(bcp)Cu]PF6 or [Ru(bpy)3](BF4)2. reactions proceed smoothly, affording desired alanines in up 99% yield when diethyl 1,4-dihydro-2,6-dimethyl-3,5-pyridinedicarboxylate [Hantzsch ester (HE)] used as an additive. N,N-Diisopropylethylamine (DIPEA) has been selected reductant both protocols. A mechanistic study means transient absorption spectroscopy unveils halogen-atom transfer (XAT) process formation.

Language: 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, Journal Year: 2024, Volume and Issue: 89(14), P. 10175 - 10179

Published: July 8, 2024

Herein, we disclose a general method for the assembly of

Language: Английский

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Radical C‐Glycosylation Using Photoexcitable Unprotected Glycosyl Borate

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Aug. 23, 2024

Abstract We have developed radical C‐glycosylation using photoexcitable unprotected glycosyl borate. The direct excitation of borate under visible light irradiation enabled the generation anomeric without any photoredox catalysts. in situ generated was applicable to addition such as Giese‐type and Minisci‐type reaction introduce alkyl heteroaryl groups at position. In addition, radical–radical coupling between acyl imidazolide provided C‐glycosides.

Language: Английский

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Diversification of Glycosyl Compounds via Glycosyl Radicals

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(38)

Published: June 7, 2023

Abstract Glycosyl radical functionalization is one of the central topics in synthetic carbohydrate chemistry. Recent advances metal‐catalyzed cross‐coupling chemistry and metallaphotoredox catalysis provided powerful platforms for glycosyl diversification. In particular, discovery new precursors conjunction with these advanced reaction technologies have significantly expanded space compound synthesis. this Review, we highlight most recent progress area starting from 2021, reports included will be categorized based on different types better clarity.

Language: Английский

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