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

Yu-Jun Ruan,

Xiaoli Wang, Pengfei Wang

et al.

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

Zirconaaziridine-Mediated Ni-Catalyzed Diastereoselective C(sp2)-Glycosylation DOI
Yu Gan,

Jun‐Feng Zhou,

Xuejiao Li

et al.

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

Citations

8
Synthesis of 2-Indolyl C-Glycoside Neopetrosins A and C and Congeners via Ni-Catalyzed Photoreductive Cross-Coupling DOI
Yan Xia, Yingjie Wang, Zhaolun Zhang

et al.

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

Citations

15
Visible-Light-Mediated Synthesis of C-Alkyl Glycosides via Glycosyl Radical Addition and Aryl Migration DOI

Rui-Qiang Jiao,

Yanan Ding,

Ming Li

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(33), P. 6099 - 6104

Published: Aug. 14, 2023

A visible-light-induced glycoarylation of activated olefins has been accomplished. Glycosyl radicals are generated via radical transfer strategies between (TMS)3SiOH and glycosyl bromides. Subsequent translocation rapid 1,4-aryl migration form β-sugar amide derivatives, eight types sugars compatible with this reaction. Further, the cascade reaction produced a quaternary carbon center good functional group adaptability high regioselectivity in mild conditions.

Language: Английский

Citations

14
Electrochemical Glycosylation via Halogen-Atom-Transfer for C-Glycoside Assembly DOI Creative Commons
Jun Wu, Purushothaman Rajeshwaran,

Felix Kallert

et al.

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

Citations

5
Direct Construction of C‐Alkyl Glycosides from Non‐Activated Olefins via Nickel‐Catalyzed C(sp3)─C(sp3) Coupling Reaction DOI Creative Commons
Changyue Yu,

Y. Wen Xu,

Mingjie Zeng

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: 11(12)

Published: Jan. 18, 2024

Among C-glycosides, C-alkyl glycosides are significant building blocks for natural products and glycopeptides. However, research on efficient construction methods remains relatively limited. Compared with Michael acceptors, non-activated olefins more challenging substrates have rarely been employed in the of C-glycosides. Here, a highly convenient approach synthesis through nickel-catalyzed C(sp

Language: Английский

Citations

4
Pd-Catalyzed Stereospecific Glycosyl Cross-Coupling of Reversed Anomeric Stannanes for Modular Synthesis of Nonclassical C-Glycosides DOI Creative Commons
Cheng Guo-qiang, Bo Yang, Zhi Yang

et al.

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

Citations

4
Stereoselective Construction of Multifunctional C-Glycosides Enabled by Nickel-Catalyzed Tandem Borylation/Glycosylation DOI
Xiaomei Wu, Shijia Li, Liqin Chen

et al.

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

Citations

4
Rh(II) and Chiral Phosphoric Acid Co-catalyzed Selective O–H Insertions for Stereodivergent O-Alkylation of Glycosides DOI
Jicheng Wu,

Peijing Jia,

Hua Tang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 10, 2025

Carbohydrates are synthetically challenging molecules with essential biological functions in all living systems. The selective synthesis and modification of carbohydrates crucial for investigating their functions. Controlling chemo-, regio-, stereoselectivity is a central theme carbohydrate synthesis. Achieving the full set stereoisomers derivatives would significantly enhance efficiency building compound libraries studies drug discovery. However, functionalization seemingly identical hydroxyl groups remains long-standing challenge organic chemistry. In synthesis, achieving precise control both relative configurations catalyst-controlled reactions that create new stereocenter presents significant synthetic challenge. Herein, we developed an efficient method stereodivergent O-alkylation via Rh(II)/chiral phosphoric acid-cocatalyzed insertion metal carbenoids. This system mild robust, offering excellent selectivity across broad range substrates high regio- stereoselectivity. Furthermore, this strategy opens up vast opportunities

Language: Английский

Citations

0
One‐Step Aqueous Synthesis of Glycosyl Pyridinium Salts, Electrochemical Study, and Assessment of Utility as Precursors of Glycosyl Radicals Using Photoredox Catalysis DOI Creative Commons
Daniel Chong, Paula A. Brooksby, Antony J. Fairbanks

et al.

ChemistryOpen, Journal Year: 2025, Volume and Issue: unknown

Published: April 21, 2025

A single step method for the production of unprotected glycosyl pyridinium salts has been developed involving treatment sugar with a pyridine, triethylamine, and either 2‐chloro‐1,3‐dimethylimidazolinium chloride (DMC) or 2‐chloro‐1,3‐dimethyl‐1 H‐benzimidazol‐3‐ium (CDMBI) as an activator, in aqueous solution. Reaction efficiency is sensitive to steric effects, particular, ortho ‐substitution pyridine ring significantly decreased conversion product; para well tolerated. Cyclic voltammetry reveals that possess reduction potentials range −0.9 −1.4 V versus standard calomel electrode, which are modulated by electron effects substituents. However, pyridiniums not found be useful precursors radicals under photoredox conditions.

Language: Английский

Citations

0
Diversification of Glycosyl Compounds via Glycosyl Radicals DOI Creative Commons
Yi Jiang, Yijun Zhang,

Boon Chong Lee

et al.

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

Citations

10