Electrochemical nickel-catalyzed cross-coupling of glycosyl thiols with preactivated phenols and ketones

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(18), С. 3597 - 3601

Опубликована: Янв. 1, 2024

Here we report an efficient electrochemical nickel-catalyzed cross-coupling reaction for the synthesis of S -glycosides from preactivated phenols and ketones.

Язык: Английский

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Visible-Light-Mediated Synthesis of Anomeric S-Aryl Glycosides via Electron Donor–Acceptor Complex Using Thianthrenium Salts

Molecules, Год журнала: 2025, Номер 30(6), С. 1315 - 1315

Опубликована: Март 14, 2025

S-Aryl glycosides are not only popular glycosyl donors in carbohydrate chemistry but also serve as valuable tools various biological studies, which has brought significant attention to their preparation. However, there remains a pressing need for greener synthesis methods this area. In response, mild, sustainable, and metal- photocatalyst-free electron donor–acceptor (EDA)-mediated approach synthesizing using 1-thiosugar aryl thianthrenium salt was developed. Our strategy utilizes the donor, overcoming traditional reliance on electron-rich thiols, such or carbonyl typically required forming EDA complexes.

Язык: Английский

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Advancements in Electrochemical Biosensors for Comprehensive Glycosylation Assessment of Biotherapeutics

Sensors, Год журнала: 2025, Номер 25(7), С. 2064 - 2064

Опубликована: Март 26, 2025

Proteins represent a significant portion of the global therapeutics market, surpassing hundreds billions dollars annually. Among various post-translational modifications, glycosylation plays crucial role in influencing protein structure, stability, and function. This modification is especially important biotherapeutics, where precise characterization glycans vital for ensuring product efficacy safety. Although mass spectrometry-based techniques have become essential tools glycomic analysis due to their high sensitivity resolution, complexity lengthy processing times limit practical application. In contrast, electrochemical methods provide rapid, cost-effective, sensitive alternative assessment, enabling real-time glycan structures on biotherapeutic proteins. These techniques, often used conjunction with complementary methods, offer valuable insights into profiles both isolated glycoproteins intact cells. review examines latest advancements biosensors analysis, highlighting potential enhancing biotherapeutics advancing field precision medicine.

Язык: Английский

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Exploring the Chemistry and Applications of Thio-, Seleno-, and Tellurosugars

Molecules, Год журнала: 2025, Номер 30(9), С. 2053 - 2053

Опубликована: Май 5, 2025

Given the crucial roles of carbohydrates in energy supply, biochemical processes, signaling events and pathogenesis several diseases, development carbohydrate analogues, called glycomimetics, is a key research area Glycobiology, Pharmacology, Medicinal Chemistry. Among many structural transformations explored, replacement endo- exocyclic oxygen atoms by carbon (carbasugars) or heteroatoms, such as nitrogen (aza- iminosugars), phosphorous (phosphasugars), sulfur (thiosugars), selenium (selenosugars) tellurium (tellurosugars) have garnered significant attention. These isosteric substitutions can modulate bioavailability, stability, bioactivity, while introducing new properties, redox activity, interactions with pathological lectins enzymes, cytotoxic effects. In this manuscript we focused on three major families glycomimetics: thio-, seleno-, tellurosugars. We provide comprehensive review most relevant synthetic pathways leading to primarily at endocyclic glycosidic positions. The scope includes metal-catalyzed reactions, organocatalysis, electro- photochemical transformations, free-radical automated syntheses. Additionally, mechanistic insights, stereoselectivity, biological properties are also discussed. diversity promising bioactivities these glycomimetics underscore their significance area.

Язык: Английский

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Electrooxidation-induced arylsulfonylation of xanthene derivatives with DABSO as an SO2 surrogate

Organic & Biomolecular Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

An electrochemical redox C(sp3)-H arylsulfonylation of xanthenes has been developed using aryl diazonium tetrafluoroborates and DABSO as the arylsulfone source. This radical reaction proceeds via formation arylsulfonyl radicals from between DABSO, followed by a cross-coupling process. Notably, occurs in absence any catalyst or external oxidant, providing efficient sulfonylation with broad functional group compatibility.

Язык: Английский

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Tempo-Catalyzed Electrochemical Hydrobenzylation of Imines with Methylarenes Via Radical Cascade Reaction

Опубликована: Янв. 1, 2025

Язык: Английский

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Electrochemically Benzyl Cation‐Triggered Alkylacetoxylation of Terminal Alkynes and Carboxylic Acids

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(12), С. 2721 - 2727

Опубликована: Май 11, 2024

Abstract A catalyst‐free electrochemical alkylacetoxylation reaction of terminal alkynes with (thio)xanthenes and carboxylic acids is developed. Treating the addition products K 2 CO 3 as a base in methanol affords ketones moderate to good yields. Preliminary experimental computational studies indicate that benzylic cation generated from triggers electrophilic alkynes.

Язык: Английский

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Stereoselective Synthesis of β-S-Glycosides via Palladium Catalysis

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(12), С. 8815 - 8827

Опубликована: Июнь 5, 2024

S-Glycosides are more resistant to enzymatic and chemical hydrolysis exhibit higher metabolic stability than common O-glycosides, demonstrating their widespread application in biological research drug development. In particular, β-S-glycosides used as antirheumatic, anticancer, antidiabetic drugs clinical practice. However, the stereoselective synthesis of is still highly challenging. Herein, we report an effective β-S-glycosylation using 3-O-trichloroacetimidoyl glycal thiols under mild conditions. The C3-imidate designed guide Pd form a complex with glucal from upper face, followed by Pd–S (thiols) coordination realize β-stereoselectivity. This method demonstrates excellent compatibility broad scope various thiol acceptors donors yields up 87% β/α ratio 20:1. present strategy for late-stage functionalization drugs/natural products such estrone, zingerone, thymol. Overall, this novel simple operation approach provides general practical construction β-thioglycosides, which holds high potential discovery

Язык: Английский

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Pd-Catalyzed Synthesis of 1-(Hetero)aryl Thioglycosides: Strategy for the Trapping of an Acyl Group of Glycosylthioesters by Coupling of Bis-Electrophilic–Nucleophilic Partners

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(21), С. 15777 - 15792

Опубликована: Окт. 15, 2024

Herein, we describe a stereoretentive palladium-catalyzed cross-coupling between the in situ-generated glycosyl thiolate anion and diverse (hetero)aryl iodides at room temperature for creating library of thioglycosides. The key to success is judicious pairing bis-electrophilic–nucleophilic partners with variety thioesters an atom-economical way which both acylium cation are incorporated into final analogue. advantage this method acyl transfer on various nucleophilic partners, including hydroxyl, primary or secondary amine, amino acid, biologically active hSGLT1 inhibitor.

Язык: Английский

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Electrochemically dehydrogenative C(sp²)–H/S–H cross-coupling: efficient synthesis of ortho-aminophenyl thioglycoside derivatives

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(11), С. 3041 - 3047

Опубликована: Янв. 1, 2024

A method has been reported for synthesizing aryl thioglycosides through direct electrocatalytic dehydrogenative C(sp 2 )–H/S–H cross-coupling.

Язык: Английский

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