Template Synthesis to Solve the Unreachable Ortho C–H Functionalization Reaction of Aryl Iodide DOI
Bo‐Sheng Zhang,

Wan-Yuan Jia,

Yiming Wang

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(23), P. 16539 - 16546

Published: Nov. 10, 2023

This report describes the use of a simple Pd/NBE catalytic system to achieve ortho C-H oxylation and phosphonylation other functionalizations aryl iodide through templated conversion reactions. Dimethylamine is introduced in ortho-site amination, dimethylamine quickly converted methyl quaternary ammonium salt precipitation. Methyl avoids Hofmann elimination subsequent functionalization. method solves various functionalization reactions that have not been achieved for long time field chemistry indirectly.

Language: Английский

Stereoselective assembly of C-oligosaccharides via modular difunctionalization of glycals DOI Creative Commons

Yanan Ding,

Mei-Ze Xu,

Yan‐Chong Huang

et al.

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

Citations

11
Diverse Synthesis of C-Glycosides by Stereoselective Ni-Catalyzed Carboboration of Glycals DOI
Mao‐Yun Lyu, Samuel A. Jacobo, M. Kevin Brown

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 18866 - 18872

Published: July 5, 2024

C-Glycosides are important structures that common to natural products and pharmaceutical agents. Established methods for their synthesis involve the reaction of an activated anomeric carbon. In this study, we report a conceptually new approach involves stereoselective Ni-catalyzed carboboration glycals. these reactions, not only is C–C bond formed at carbon, but synthetically useful C–B also installed. Upon oxidation, differentially protected C-glycosides be formed. addition, stereospecific manipulation leads diverse C-glycosides. Finally, application method in established C-glycosides, such as C-glycosyl amino acids, well strategy make all possible diastereomers C1 C2.

Language: Английский

Citations

8
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
Photo‐Induced Ruthenium‐Catalyzed C−H Arylation Polymerization at Ambient Temperature DOI Creative Commons
Takuya Michiyuki, Isaac Maksso, Lutz Ackermann

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(25)

Published: April 18, 2024

Transition metal-catalyzed C-H arylation polymerization (CHAP) is an attractive tool for constructing π-conjugated polymers in a sustainable manner. However, the existing methods primarily rely on palladium catalysis, which usually entails harsh reaction conditions and branching/cross-linking. Here we report first example of ambient-temperature ruthenium-catalyzed induced by visible light irradiation. The present can produce various meta- para-linked excellent yields with high molecular weights. remarkable feature our mild platform represented chemoselectivity, leading to that are otherwise inaccessible under conventional at temperatures.

Language: Английский

Citations

4
(1R)-2,3,4,6-Tetra-O-benzyl-1-C-allyl-1-deoxy-1-C-(2-thiazolyl)-D-galactopyranose DOI Creative Commons
Clark Ferrari,

Alessandro Dondoni,

Alberto Marra

et al.

Molbank, Journal Year: 2025, Volume and Issue: 2025(1), P. M1949 - M1949

Published: Jan. 8, 2025

We have previously reported that thiazolylketol acetates, synthesized by the addition of 2-lithiothiazole to sugar lactones followed acetylation, are efficient glycosyl donors affording O-, N-, P-, and C-glycosides. After first example C-glycosidation recently described us, we report here on unexpected outcome reaction a acetate with allyltrimethylsilane in presence trimethylsilyl triflate. The obtained intermediate, an intramolecular N-thiazolium salt, could be stereoselectively converted into desired allyl C-thiazolylketoside.

Language: Английский

Citations

0
Switchable and Stereospecific C-Glycosylation Strategy via Formal Functional Group Deletion DOI
Xiaoshen Ma,

Stephen J. Sujansky

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 9, 2025

Carbohydrates constitute an important class of biologically relevant natural products. Among the synthetic glycomimetics, C-glycosides are particularly interesting due to their chemical and metabolic stability toward acidic enzymatic hydrolysis at anomeric position. The stereochemical outcomes traditional methodologies access rely heavily on substrate control. Herein, we report a novel strategy diverse with precise control position via formal functional group deletion, where both α- β-anomers furanoses pyranoses can be obtained as single stereoisomers. Additionally, broad scope heterocyclic this further illustrates its potential for empowering future application in biology research drug discovery.

Language: Английский

Citations

0
Highly Stereoselective Synthesis of Bis-C-ferrocenyl Glycosides via Palladium-Catalyzed Directed C–H Glycosylation DOI
Zhuo‐Zhuo Zhang, Lu Jiang, Jun‐Long Li

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(22), P. 4070 - 4074

Published: May 26, 2023

Conjugation of carbohydrates to ferrocene scaffolds is great value in drug design, given the nontoxic and lipophilic nature ferrocene. However, efficient stereoselective synthesis C-ferrocenyl glycosides remains a challenge. Herein, we developed Pd-catalyzed C-H glycosylation provide rapid access sole bis-C-ferrocenyl good high yields (up 98% yield) with exclusive stereoselectivity. A diverse range glycosyl chlorides were well tolerated, including d-mannose, d-glucose, l-xylose, l-rhamnose, d-mannofuranose, d-ribofuranose. Additionally, mononuclear PdII intermediate was characterized by X-ray single-crystal diffraction, might participate palladation step.

Language: Английский

Citations

9
Synthesis of heteroaryl C-glycosides via Ru-catalyzed C–H activation/cyclization: dioxazolone glycogen designs and applications DOI

Deng-Yin Liu,

Pengfei Wang,

Xin-Yue Hu

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(13), P. 3609 - 3613

Published: Jan. 1, 2024

New glycogen reagents of dioxazolone anomers have been developed. The versatile heteroarene C -glycosides synthesized using a Ru-catalyzed C–H activation/annulation strategy, employing these anomers.

Language: Английский

Citations

3
Assembly of Heterocyclic C-Glycosides by Ru-Catalyzed C–H Activation/Cyclization with Carbonyl Sulfoxonium Ylide Glyco-Reagents DOI

Deng-Yin Liu,

Pengfei Wang,

Yu-Jun Ruan

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(24), P. 5092 - 5097

Published: June 7, 2024

New carbonyl sulfoxonium ylide glyco-reagents have been developed, enabling the synthesis of versatile heteroarene C-glycosides through a Ru-catalyzed C–H activation/annulation strategy. These reactions tolerate various saccharide donors and represent significant advance in stereoselective heterocyclic C-glycosides. Furthermore, strategy methods could be applied to large-scale late-stage modifications some structurally complex natural products or drugs.

Language: Английский

Citations

2