Chemical synthesis of oligosaccharides and their application in new drug research

European Journal of Medicinal Chemistry, Год журнала: 2023, Номер 249, С. 115164 - 115164

Опубликована: Фев. 1, 2023

Язык: Английский

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

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(32), С. 22413 - 22423

Опубликована: Авг. 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.

Язык: Английский

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Nickel-Catalyzed 1,1-Carboboration of Polysubstituted Internal Alkenes

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 1, 2025

Herein, we report a nickel-catalyzed 1,1-carboboration of di- and trisubstituted alkenyl boronates through chain-walking strategy. This reaction effectively addresses the polarity-mismatch problem via ligand control, enabling coupling various carbon-based electrophiles while accommodating broad range functional groups. The approach yields diverse tetrasubstituted carbon gem-diboronate derivatives with exceptional regioselectivity. synthetic utility this method is further demonstrated concise synthesis high-value bioactive molecules.

Язык: Английский

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Development of α-Selective Glycosylation with l-Oleandral and Its Application to the Total Synthesis of Oleandrin

Organic Letters, Год журнала: 2023, Номер 25(6), С. 966 - 971

Опубликована: Фев. 5, 2023

This letter describes the development of an α-selective glycosylation using l-oleandrose, a 2-deoxysugar that is frequently found in natural products, and its application to total synthesis cardiotonic steroids oleandrin beaumontoside. To improve reaction diastereoselectivity minimize side-product formation, extensive evaluation optimization conditions leading digitoxigenin with l-oleandrose-based donors was conducted. These studies led exploration 8 different phosphine·acid complexes or salts yielded HBr·PPh3 as optimal catalyst, which provided cleanest α-glycosylation produced protected beaumontoside 67% yield. Subsequent these synthetic oleandrigenin afforded desired α-product 69% isolated yield─enabling completion first 17 steps (1.2% yield) from testosterone.

Язык: Английский

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Glycosylidene-carbene-mediated homologation of boronic esters for the synthesis of boro-ketosides

Chem Catalysis, Год журнала: 2024, Номер 4(4), С. 100946 - 100946

Опубликована: Март 8, 2024

Язык: Английский

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Asymmetric Organocatalytic Homologation: Access to Diverse Chiral Trifluoromethyl Organoboron Species

Chemistry - A European Journal, Год журнала: 2022, Номер 28(58)

Опубликована: Авг. 18, 2022

Abstract A broad range of aliphatic, aromatic, and heterocyclic boronic acids were successfully homologated using trifluorodiazoethane in the presence BINOL derivatives to provide corresponding chiral trifluoromethyl containing acid high yields excellent enantioselectivity. The situ conversion transient alcohols or β ‐CF3 carboxylates are also demonstrated.

Язык: Английский

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Transition-Metal-Free Insertion of Diazo Compounds, N-Arylsulfonylhydrazones or Ylides into Organoboronic Acids or Their Derivatives

Synlett, Год журнала: 2023, Номер 34(18), С. 2071 - 2084

Опубликована: Июнь 5, 2023

Abstract Insertion reactions of carbenes or ylides with organoboronic acids their derivatives have emerged as valuable methods for coupling homologation organoboron compounds under metal-free conditions. The crucial steps these are coordination the electron-rich carbon centers carbene precursors to electron-poor boron center, followed by 1,2-migration corresponding tetracoordinated intermediates. This type unique transformation provides an efficient method construction C–C C–X (X = H, B) bonds. Moreover, C–B bonds generated such transformations can be utilized a handle further derivatization iterative homologations. In this Account, we summarize developments in arena according reactive diazo compound, N-arylsulfonylhydrazone ylide species involved. 1 Introduction 2 Reactions Diazo Compounds 3 N-Arylsulfonylhydrazones 4 Ylides 5 Conclusion

Язык: Английский

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Nickel-Catalyzed Reductive Decarboxylative/Deaminative Glycosylation of Activated Aliphatic Acids and Primary Amines

Organic Letters, Год журнала: 2023, Номер 25(27), С. 5022 - 5026

Опубликована: Июль 3, 2023

This study describes the nickel-catalyzed reductive decarboxylative/deaminative glycosylation of activated aliphatic acids/amines. Various alkyl C-glycosides were efficiently constructed under simple and mild reaction conditions. The reactions high-yielding exhibited a broad substrate scope, thereby enabling transformation some structurally complex natural products late-stage modifications drugs.

Язык: Английский

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Stereospecific Palladium-Catalyzed Direct Glycosylation of Oximes: Access to N–O-Linked Glycosides

Organic Letters, Год журнала: 2023, Номер 25(22), С. 4177 - 4182

Опубликована: Май 30, 2023

A highly efficient, palladium-catalyzed glycosylation between 3,4-O-carbonate glycals and acid-labile oximes is disclosed. This approach features broad substrate scope, high functional group tolerance, easy scalability, delivering glycosyl in excellent yields with exclusive β-selectivity retention of Z/E geometries. The power this method demonstrated by a set site-selective transformations products late-stage glycodiversification bioactive molecules. Overall, our strategy provides an efficient toolkit for facile access to valuable N-O-linked glycosides.

Язык: Английский

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Facile and stereospecific synthesis of diverse β-N-glycosyl sulfonamide scaffolds via palladium catalysis

Chemical Communications, Год журнала: 2023, Номер 59(86), С. 12907 - 12910

Опубликована: Янв. 1, 2023

Glycosylation is an important strategy to improve the druggability of lead compounds. Here, we present a palladium-catalysed stereospecific N-glycosylation sulfonamides. This approach stands out with wide substrate scope, high functional group tolerance, and easy scalability, furnishing broad spectrum densely functionalized β-N-glycosyl sulfonamides good efficiency exceptional regio-/stereoselectivity. Diverse drug-like glycosulfonamido scaffolds have been constructed via late-stage diversification various facile synthetic transformations products. Collectively, established protocol provides valuable tool for efficiently preparing glycosyl facilitate drug discovery.

Язык: Английский

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