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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N-glycoside synthesis through combined copper- and photoredox-catalysed N-glycosylation of N-nucleophiles

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(5), P. 623 - 632

Published: March 1, 2024

Language: Английский

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StereoselectiveC‐Aryl Glycosylation by Catalytic Cross‐Coupling of Heteroaryl Glycosyl Sulfones

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(18)

Published: March 7, 2023

Stereoselective C-glycosylation reactions are increasingly gaining attention in carbohydrate chemistry because they enable glycosyl precursors, readily accessible as anomeric mixtures, to converge a single diastereomeric product. However, controlling the stereochemical outcome through transition-metal catalysis remains challenging, and methods that leverage bench-stable heteroaryl sulfone donors facilitate glycosylation rare. Herein, we show two complementary nonprecious metal catalytic systems, based on iron or nickel, which capable of promoting efficient C-C coupling between sulfones aromatic nucleophiles electrophiles distinct mechanisms modes activation. Diverse C-aryl glycosides were secured with excellent selectivity, scope, functional-group compatibility, reliable access both α β isomers was possible for key sugar residues.

Language: Английский

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Stereoselective assembly of C-oligosaccharides via modular difunctionalization of glycals

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: March 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.

Language: Английский

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Stereoselective and site-divergent synthesis of C-glycosides

Nature Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 13, 2024

Language: Английский

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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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Zirconaaziridine-Mediated Ni-Catalyzed Diastereoselective C(sp²)-Glycosylation

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(24), P. 16753 - 16763

Published: June 11, 2024

In the realm of organic synthesis, catalytic and stereoselective formation C-glycosidic bonds is a pivotal process, bridging carbohydrates with aglycones. However, inherent chirality saccharide scaffold often has substantial impact on stereoinduction imposed by chiral ligand. this study, we have established an unprecedented zirconaaziridine-mediated asymmetric nickel catalysis, enabling diastereoselective coupling bench-stable glycosyl phosphates range (hetero)aromatic glycal iodides as feasible electrophiles. Our developed method showcases broad scope high tolerance for various functional groups. More importantly, precise stereocontrol toward both anomeric configurations forming C(sp2)-glycosides can be realized simply utilizing popular bioxazoline (biOx) ligands in reductive Ni catalysis. Regarding operating mechanism, experimental computational studies support occurrence redox transmetalation leading to transient, bimetallic Ni–Zr species that acts potent efficient single-electron reductant process.

Language: Английский

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Palladium-catalyzed Suzuki-Miyaura cross-couplings of stable glycal boronates for robust synthesis of C-1 glycals

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: June 19, 2024

Abstract C- 1 Glycals serve as pivotal intermediates in synthesizing diverse C -glycosyl compounds and natural products, necessitating the development of concise, efficient user-friendly methods to obtain glycosides is essential. The Suzuki-Miyaura cross-coupling glycal boronates notable for its reliability non-toxic nature, but donor stability remains a challenge. Herein, we achieve significant breakthrough by developing stable boronates, effectively overcoming issue glycal-based Suzuki–Miyaura coupling. Leveraging balanced reactivity our establish robust palladium-catalyzed reaction, facilitating formation various C( sp 2 )-C( ), 3 ) bonds under mild conditions. Notably, expand upon this achievement DNA-compatible reaction synthesize glycal-DNA conjugates. With excellent reactivity, stability, generality, ease handling, method holds promise widespread appication preparation products.

Language: Английский

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Synthesis of 2-Indolyl C-Glycoside Neopetrosins A and C and Congeners via Ni-Catalyzed Photoreductive Cross-Coupling

Organic Letters, Journal Year: 2023, Volume and Issue: 25(36), P. 6741 - 6745

Published: Aug. 30, 2023

The synthesis of neopetrosins A and C, two 2-indolyl C-α-d-mannopyranosides, their congeners has been realized via a direct Ni/photoredox-catalyzed reductive coupling 3-methoxycarbonyl-2-iodo-1H-indoles with pyranosyl bromides.

Language: Английский

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Electrochemical Glycosylation via Halogen-Atom-Transfer for C-Glycoside Assembly

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(15), P. 11532 - 11544

Published: July 19, 2024

Glycosyl donor activation emerged as an enabling technology for anomeric functionalization, but aimed primarily at O-glycosylation. In contrast, we herein disclose mechanistically distinct electrochemical glycosyl bromide activations via halogen-atom transfer and C-glycosylation. The radical addition to alkenes led C-alkyl glycoside synthesis under precious metal-free reaction conditions from readily available bromides. robustness of our e-XAT strategy was further mirrored by C-aryl C-acyl glycosides assembly through nickela-electrocatalysis. Our approach provides orthogonal with expedient scope, hence representing a general method direct C-glycosides assembly.

Language: Английский

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