Palladium-Catalyzed Regio- and Stereoselective Glycosylation of Azole Heterocycles Enables Access to Diverse Heterocyclic N-Glycosides

Organic Letters, Journal Year: 2024, Volume and Issue: 26(32), P. 6878 - 6883

Published: Aug. 6, 2024

An efficient and practical glycosylation platform for synthesizing

Language: Английский

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Stereoselective synthesis of 2-deoxy-α-C-glycosides from glycals

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: 35(12), P. 109674 - 109674

Published: Feb. 29, 2024

Language: Английский

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Pd-Catalyzed Stereospecific Glycosyl Cross-Coupling of Reversed Anomeric Stannanes for Modular Synthesis of Nonclassical C-Glycosides

Precision Chemistry, Journal Year: 2024, Volume and Issue: 2(11), P. 587 - 599

Published: July 21, 2024

Nonclassical C-glycosides, distinguished by their unique glycosidic bond connection mode, represent a promising avenue for the development of carbohydrate-based drugs. However, accessibility nonclassical C-glycosides hinders broader investigations into structural features and modes action. Herein, we present first example Pd-catalyzed stereospecific glycosylation anomeric stannanes with aryl or vinyl halides. This method furnishes desired in good to excellent yields, while allowing exclusive control configuration. Of significant note is demonstration generality practicality this C-glycosylation approach across more than 50 examples, encompassing various protected unprotected saccharides, deoxy sugars, oligopeptides, complex molecules. Furthermore, biological evaluation indicates that modifications drug molecules can positively impact activity. Additionally, extensive computational studies are conducted elucidate rationale behind differences reaction reactivity, unveiling transmetalation transition state containing silver (Ag) within six-membered ring. Given its remarkable controllability, predictability, consistently high chemical selectivity stereospecificity regarding carbon Z/E configuration, outlined study offers solution longstanding challenge accessing stereocontrol.

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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Palladium-Catalyzed Stereospecific Glycosylation Enables Divergent Synthesis of N–O-Linked Glycosides

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 9, 2025

We present a versatile palladium-catalyzed glycosylation platform that enables facile access to structurally diverse N-O-linked glycosides with constantly excellent regio- and stereoselectivities. Importantly, this approach offers broad substrate scope, low catalyst loadings, outstanding chemoselectivity, allowing for the selective reaction of oximes/hydroximic acids over hydroxyl groups would otherwise pose challenges in conventional methods. The synthetic utility method is further exemplified through range transformations late-stage modification bioactive molecules. Overall, our provides an efficient toolkit synthesis glycosides, which will facilitate their subsequent biological evaluations.

Language: Английский

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Diversification of Glycosyl Compounds via Glycosyl Radicals

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(38)

Published: June 7, 2023

Abstract 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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Nickel and Chiral Phosphoric Acid Cocatalysis Enables Synthesis of C-Acyl Glycosides

Organic Letters, Journal Year: 2024, Volume and Issue: 26(7), P. 1332 - 1337

Published: Feb. 8, 2024

We disclosed a Ni/CPA cocatalyzed protocol to access diverse C-acyl glycosides under mild conditions with broad functional group compatibility through the coupling of readily available glycosyl bromides and carboxylic esters. The potential application methodology was demonstrated by glycosylation bioactive molecules transformation products variety value-added molecules. Mechanistic studies revealed that CPA might serve as bifunctional H-bond catalyst activate esters nickel catalyst.

Language: Английский

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Recent advances in stereoselective synthesis of non-classical glycosides

Tetrahedron Chem, Journal Year: 2024, Volume and Issue: 9, P. 100068 - 100068

Published: Feb. 24, 2024

Language: Английский

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Visible-Light-Promoted Thiolation of Benzyl Chlorides with Thiosulfonates via a Photoactive Electron Donor–Acceptor Complex

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(13), P. 9450 - 9461

Published: June 13, 2024

Visible-light-promoted thiolation of benzyl chlorides with thiosulfonates is disclosed via an electron donor-acceptor complex strategy. In addition to efficiently delivering a series arylbenzylsulfide compounds, versatile thioglycosides were also successfully constructed by applying the metal- and photocatalyst-free protocol. Preliminary mechanistic studies suggest that radical-radical coupling process was involved in this transformation.

Language: Английский

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Cobalt-Catalyzed Cross-Coupling of Glycosyl Sulfones with Zinc reagents toward the Stereoselective Synthesis of C(sp/sp²)-Glycosides

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 18, 2025

A cobalt-catalyzed desulfonylative cross-coupling of glycosyl sulfones with organozinc reagents toward the stereoselective synthesis C-glycosides is reported. The new C-glycoside proceeds under mild reaction conditions and exhibits tolerance to a range functional groups. Diverse alkynylated, arylated, alkenylated products are formed high efficiency excellent diastereoselectivity. Mechanistic studies indicate radical pathway.

Language: Английский

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