Diversification of Glycosyl Compounds via Glycosyl Radicals

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(38)

Опубликована: Июнь 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.

Язык: Английский

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Recent advances in transition-metal-catalyzed glycosyl cross-coupling reactions

Chem Catalysis, Год журнала: 2022, Номер 2(12), С. 3430 - 3470

Опубликована: Ноя. 8, 2022

Язык: Английский

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Ligand‐Controlled Stereoselective Synthesis of 2‐Deoxy‐β‐C‐glycosides by Cobalt Catalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(22)

Опубликована: Март 17, 2023

2-Deoxy-β-C-glycosides represent an important class of carbohydrates that are present in many bioactive molecules. However, owing to the lack substituents at C2 position, stereoselective synthesis 2-deoxy-β-C-glycosides is highly challenging. Herein, we report a ligand-controlled C-alkyl glycosylation reaction access 2-deoxy-β-C-alkyl glycosides from readily available glycals and alkyl halides. This method exhibits broad substrate scope excellent diastereoselectivity under very mild conditions. In addition, unprecedented stereodivergent 2-deoxy-C-ribofuranosides achieved using different chiral bisoxazoline ligands. Mechanistic studies suggest hydrometallation glycal with bisoxazoline-ligated Co-H species may be turnover-limiting stereodetermining step this transformation.

Язык: Английский

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C‐GlycosideSynthesis Enabled by Nickel Catalysis

Chinese Journal of Chemistry, Год журнала: 2023, Номер 41(17), С. 2217 - 2236

Опубликована: Апрель 13, 2023

Comprehensive Summary C‐Glycosides are critical, naturally occurring products and medicinal candidates, extensive efforts have been made to explore efficient approaches for creating C‐glycosidic bonds. Transition‐metal‐catalysis, particularly nickel‐catalyzed C‐glycosylation reactions constitute a promising strategy. However, achieving stereoselective synthesis of α‐ β‐C‐glycosides has long‐standing challenge. To address this problem, variety nickel‐mediated strategies developed. This review highlights recent developments in the diastereoselective briefly summarizes mechanistic understandings these methods.

Язык: Английский

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Domino meta ‐C−H Ethyl Glycosylation by Ruthenium(II/III) Catalysis: Modular Assembly of meta‐C ‐Alkyl Glycosides

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(20)

Опубликована: Фев. 24, 2023

Glycosyl anomeric radical addition reactions have been well-explored and proved efficient for the C-alkyl glycosides synthesis, but multicomponent Domino transformations rapid controllable construction of structurally diversified in a single step are still rare. In contrast, we, herein, report ruthenium(II)-catalyzed meta-C-H ethyl glycosylation, enabling challenging meta-C-alkyl glycosides. Our ruthenium(II) catalysis was reflected by mild reaction condition, exclusive meta-site selectivity high levels selectivity. addition, glycosylation allowed synthesis versatile 1,2-trans-C-alkyl with commercially available vinyl arenes, acrylates easily accessible glycosyl bromides.

Язык: Английский

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Synthesis of C‐Aryl Glycosides by C−H Functionalization

Chemistry - A European Journal, Год журнала: 2023, Номер 29(32)

Опубликована: Март 21, 2023

Abstract In recent years, the synthesis of C‐aryl glycosides hrough C−H functionalization has attracted extensive attention organic chemists due to its steps and atomic economy. this concept, we systematically summarizes with diverse regioselectivity diastereoselectivity from perspective arylation glycosylation arenes. It can be found that a series recently developed reactions have higher site‐selectivity diastereomeric selectivity than Friedel–Crafts reaction. The reaction conditions are milder, which compatible acid‐sensitive protective groups, such as acetals or ketals, deprotection is more convenient. seen there few reports on remote aromatic hydrocarbons, new field needs further research. addition, lot shortcomings, need explored: a) precise regulation stereoselectivity in process also optimization; b) research mechanism almost limited DFT calculation, no exact experimental evidence. For key parts, specific between cyclo‐metal intermediates glycosyl donors ortho ‐C Ar −H still unclear; c) fact aryl glycoside compounds contain bare hydroxyl groups practical applications, it an urgent problem realize compatibility substrates containing naked remove by mild efficient method after reaction; d) rapidly developing field, study greener, economical arenes future, will conducive biological application significance.

Язык: Английский

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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 assembly of C-oligosaccharides via modular difunctionalization of glycals

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

Опубликована: Март 30, 2024

Abstract C-oligosaccharides are found in natural products and drug molecules. Despite the considerable progress made during last decades, modular stereoselective synthesis of continues to be challenging underdeveloped compared technology O-oligosaccharides. Herein, we design a distinct strategy for efficient via palladium-catalyzed nondirected C1–H glycosylation/C2-alkenylation, cyanation, alkynylation 2-iodoglycals with glycosyl chloride donors while realizing difunctionalization 2-iodoglycals. The catalysis approach tolerates various functional groups, including derivatives marketed drugs products. Notably, obtained can further transformed into C-glycosides fully conserving stereochemistry. results density theory (DFT) calculations support oxidative addition mechanism alkenyl-norbornyl-palladacycle (ANP) intermediate α-mannofuranose high stereoselectivity glycosylation is due steric hindrance.

Язык: Английский

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Enantioselective C−H Bond Functionalization Involving Arene Ruthenium(II) Catalysis

Chemistry - A European Journal, Год журнала: 2022, Номер 29(7)

Опубликована: Окт. 27, 2022

The p-Cymene ruthenium(II) complex is one of the most widely used catalysts in C-H activation. However, enantioselective activation promoted by arene complexes has not been realized until recently. revealed strategies include intramolecular nitrene insertion, use chiral transient directing groups, carboxylic acid, relay catalysis, and ligands. In this minireview, these advances are summarized discussed hope spurring further developments.

Язык: Английский

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Catalytic Multicomponent Synthesis ofC‐Acyl Glycosides by Consecutive Cross‐Electrophile Couplings

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(46)

Опубликована: Сен. 27, 2022

C-Acyl glycosides are versatile intermediates to natural products and medicinally relevant entities. Conventional cross-coupling strategies secure these molecules often relied on two-component manifolds in which a glycosyl precursor is coupled with an acyl donor (pre-synthesized or generated situ) under transition metal dual catalysis forge C-C bond. Here, we disclose three-component Ni-catalyzed reductive regime that facilitates the chemoselective union of halides, organoiodides commercially available isobutyl chloroformate as CO surrogate. The method tolerates multiple functionalities resulting obtained high diastereoselectivities. Theoretical calculations provide mechanistic rationale for unexpectedly chemoselectivity sequential cross-electrophile couplings. This approach enables expeditious assembly difficult-to-synthesize C-acyl glycosides, well late-stage keto-glycosylation oligopeptides.

Язык: Английский

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