Stereoretentive Conversion to C-Glycosides from S-Glycosides via Ligand-Coupling on Sulfur(IV)

Organic Letters, Journal Year: 2025, Volume and Issue: 27(4), P. 954 - 960

Published: Jan. 21, 2025

A novel strategy is reported for the stereoselective synthesis of C(sp2)-C(sp3) C-glycosides, which converts heteroaryl S-glycosides into C-glycosides with retention configuration through a sequential process involving oxidation and Grignard reagent attack. The new method involves generation S(IV) intermediate, followed by ligand coupling glycosyl groups to yield C-glycosides. diverse were achieved good efficiency.

Language: Английский

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Stereoselective Construction of Multifunctional C-Glycosides Enabled by Nickel-Catalyzed Tandem Borylation/Glycosylation

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(32), P. 22413 - 22423

Published: Aug. 3, 2024

Stereochemically pure saccharides have indispensable roles in fields ranging from medicinal chemistry to materials science and organic synthesis. However, the development of a simple, stereoselective, efficient glycosylation protocol access α- β-C-glycosides (particularly 2-deoxy entities) remains persistent challenge. Existing studies primarily focused on C1 modification carbohydrates transformation glycosyl radical precursors. Here, we innovate by harnessing situ generated glycosyl-Ni species achieve one-pot borylation cascade manner, which is enabled an earth-abundant nickel-catalyzed carboboration readily accessible glycals without any ligand. This work reveals potential for modular multifunctional platform facilitate simultaneous introduction C-C C-B bonds at stereogenic center saccharides, largely unexploited research area. Preliminary experimental computational indicate that endocyclic O C3 group play important stereoseclectively forging glycosidic bonds. As result, diverse range C-R (R = alkyl, aryl, alkenyl) 2-deoxygenated glycosides bearing modifiable boron groups could be rapidly made with excellent stereocontrol exhibit remarkable functional tolerance. The synthetic underscored late-stage natural products commercial drugs as well facile preparation various rare sugars, bioactive conjugates, key intermediates prorocentin, phomonol, aspergillide A.

Language: Английский

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Efficient Iron-Catalyzed Site/Regioselective Phosphinoylation of Carbohydrates

Organic Letters, Journal Year: 2025, Volume and Issue: 27(6), P. 1555 - 1560

Published: Jan. 31, 2025

The selective incorporation of phosphorus groups into sugar molecules holds substantial synthetic and biological significance, yet this area research remains largely unexplored. In study, we successfully devised a novel method employing an efficient Fe(III) catalyst for achieving site/regioselective phosphorylation/phosphinoylation carbohydrates. This methodology boasts several merits, including mild reaction conditions, the employment cost-effective readily available catalysts, exceptional selectivity. approach provides new perspectives valuable tools functional modification molecules.

Language: Английский

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Radical dehydroxylative C-glycosylation of 1-hydroxycarbohydrates enabled by photoredox catalysis

Green Synthesis and Catalysis, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

Language: Английский

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Visible light induced palladium-catalyzed Suzuki–Miyaura cross-coupling of glycosyl chlorides to form C-aryl glycosides

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(18), P. 5044 - 5053

Published: Jan. 1, 2024

A powerful method is developed utilizing excited-state palladium-catalyzed Suzuki–Miyaura reaction to synthesize C -aryl glycosides. It can be applied a wide range of aryl and heteroaryl boronic ester substrates as well glycosyl chlorides.

Language: Английский

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ZnI2-Mediated cis-Glycosylations of Various Constrained Glycosyl Donors: Recent Advances in cis-Selective Glycosylations

Molecules, Journal Year: 2024, Volume and Issue: 29(19), P. 4710 - 4710

Published: Oct. 4, 2024

An efficient and versatile glycosylation methodology is crucial for the systematic synthesis of oligosaccharides glycoconjugates. A direct intermolecular an indirect intramolecular have been developed, former can be applied to medium-to-long-chain glycans like that nucleotides peptides. The development a generally applicable approach stereoselective construction glycosidic bonds remains major challenge, especially 1,2-

Language: Английский

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Investigating the photoactivity of low-valent zirconium catalyst in ether activation

Synlett, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 29, 2024

Abstract The cross-coupling of two distinct C(sp3 )–O bonds provides a highly valuable pathway for the construction )–C(sp3 ) bonds, but it remains underdeveloped. Recently, we reported an innovative photoinduced Zr-catalyzed carbomagnesiation reductive coupling ethers with high cross-selectivity. Mechanistic investigation reveals that photoexcitation low-valent zirconocene facilitates activation benzylic ethers. This leads to formation functionalized Grignard reagents downstream aliphatic through SN2-like pathway. 1 Introduction 2 Concept Our Design on this Work 3 Photoinduced Zr-Catalyzed Cross-Coupling Ethers 4 Benzylic Magnesium Alkoxide 5 Methods Mechanism Investigation 6 Conclusion

Language: Английский

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Selective Ni(I)/Ni(III) Process for Consecutive Geminal C(sp³)–C(sp²) Bond Formation

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 13, 2024

Ni-catalyzed multicomponent cross-couplings have emerged as a powerful strategy for efficiently constructing complex molecular architectures from diverse array of organic halides. Despite its potential, selectively forming multiple chemical bonds in single operation, particularly the realm cross-electrophile coupling catalysis, remains significant challenge. In this study, we developed consecutive open-shell reductive Ni enabling formation two geminal C(sp

Language: Английский

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