Synthesis of C‐Oligosaccharides through Versatile C(sp3)−H Glycosylation of Glycosides DOI Creative Commons
Jun Wu,

Adelina Kopp,

Lutz Ackermann

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(11)

Published: Jan. 11, 2022

Abstract C‐ oligosaccharides are pharmacologically relevant because they more hydrolysis‐resistant than O ‐oligosaccharides. Despite indisputable advances, C ‐oligosaccharides continue to be underdeveloped, likely due a lack of efficient and selective strategies for the assembly interglycosidic C−C linkages. In contrast, we, herein, report versatile robust strategy synthesis structurally complex via catalyzed C(sp 3 )−H activations. Thus, wealth (2→1)‐ (1→1)‐ becomes readily available by palladium‐catalyzed glycoside glycosylation. The isolation key palladacycle intermediates experiments with isotopically‐labeled compounds identified trans‐ stereoselectivity activation manifold was likewise exploited diversification furanoses, pyranoses disaccharides.

Language: Английский

Progress and perspectives on directing group-assisted palladium-catalysed C–H functionalisation of amino acids and peptides DOI
Sadegh Shabani, Yuezhou Wu, Hannah G. Ryan

et al.

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(16), P. 9278 - 9343

Published: Jan. 1, 2021

Peptide modifications can unlock a variety of compounds with structural diversity and abundant biological activity. In nature, peptide modifications, such as functionalisation at the side-chain position amino acids, are performed using post-translational modification enzymes or incorporation unnatural acids. However, accessing these remains challenge for organic chemists. During past decades, selective C-H activation/functionalisation has attracted considerable attention in synthetic chemistry pathway to modification. Various directing group strategies have been discovered that assist activation. particular, bidentate groups enable tuneable reversible coordination now recognised one most efficient methods site-selective activation numerous families compounds. Synthetic chemists harnessed β- γ-positions This method expanded an effective device late stage macrocyclisation total synthesis complex natural products. this review, we discuss various β-, γ-, δ-C(sp3)-H bond reactions acids formation C-X bonds aid their application late-stage

Language: Английский

Citations

65
1,2,3-Triazoles as Biomimetics in Peptide Science DOI Creative Commons
Naima Agouram, El Mestafa El Hadrami,

Abdeslem Bentama

et al.

Molecules, Journal Year: 2021, Volume and Issue: 26(10), P. 2937 - 2937

Published: May 14, 2021

Natural peptides are an important class of chemical mediators, essential for most vital processes. What limits the potential use as drugs is their low bioavailability and enzymatic degradation in vivo. To overcome this limitation, development new molecules mimicking great importance biologically active molecules. Therefore, replacing amide bond a peptide with heterocyclic bioisostere, such 1,2,3-triazole ring, can be considered effective solution synthesis relevant peptidomimetics. These 1,2,3-triazoles may have interesting biological activity, because they behave rigid link units, which mimic electronic properties bonds show bioisosteric effects. Additionally, triazole used linker moiety to other functional groups.

Language: Английский

Citations

64
Visible‐Light‐Promoted Stereoselective C(sp3)−H Glycosylation for the Synthesis of C‐Glycoamino Acids and C‐Glycopeptides DOI

Rupeng Qi,

Chao Wang,

Zijian Ma

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(24)

Published: March 22, 2022

The glycosylative modification of peptides could improve the pharmacological properties peptide drugs and deliver them efficiently to target sites. Compared with O-/N-glycosides, C-glycosides exhibit more metabolic stability. We here disclose first example visible-light-promoted Cu-catalyzed stereoselective C-glycosylation. mild reaction conditions are compatible various carbohydrate substrates, as demonstrated a series monosaccharides disaccharide, amenable synthesis wide variety C-glycoamino acids C-glycopeptidomimetics good yields excellent stereoselectivities. dual-functional photocatalyst formed in situ via coordination glycine derivative chiral phosphine Cu complex not only catalyze photoredox process but also control stereoselectivity glycosylation reaction.

Language: Английский

Citations

62
Diastereoselective Pd-Catalyzed Anomeric C(sp3)–H Activation: Synthesis of α-(Hetero)aryl C-Glycosides DOI
Juba Ghouilem, Christine Tran, Nicolás Grimblat

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(3), P. 1818 - 1826

Published: Jan. 25, 2021

Anomeric C–H bond activation is an unsolved long-standing synthetic challenge. Herein, we report a diastereoselective Pd-catalyzed anomeric C(sp3)–H methodology that allows the synthesis of elusive C-(hetero)aryl glycosides with exclusive α-selectivity.

Language: Английский

Citations

57
Late-stage stitching enabled by manganese-catalyzed C─H activation: Peptide ligation and access to cyclopeptides DOI Creative Commons
Nikolaos Kaplaneris, Felix Kaltenhäuser, Giedre Sirvinskaite

et al.

Science Advances, Journal Year: 2021, Volume and Issue: 7(9)

Published: Feb. 26, 2021

Earth-abundant manganese catalyst enabled the expedient synthesis of cyclic peptides via activation inert C─H bonds.

Language: Английский

Citations

57
Transition-Metal-Catalyzed C–C Bond-Forming Reactions via C–H Activation for the Development of Fluorescent Materials with Practical Value DOI

Kangmin Wang,

Jingxian Zhang,

Ruike Hu

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(5), P. 2796 - 2820

Published: Feb. 14, 2022

Fluorescent materials of practical value have attracted considerable attention because their important applications in the fields bioprobes, chemosensors, organic light-emitting diodes, field-effect transistors, memory devices, security systems, etc. As such, these been improving quality our daily life. In past few decades, chemists and scientists constructed various fluorescent molecules using transition-metal-catalyzed C–C bond-forming reactions via C–H activation. This approach provides a unique opportunity for efficient straightforward access to frameworks that cannot be easily by traditional synthetic routes. Review aims highlight help better understand recent development activation optimized value. addition, some perspectives on challenges opportunities this field will discussed.

Language: Английский

Citations

49
Late‐stage C−H Functionalization of Tryptophan‐Containing Peptides with Thianthrenium Salts: Conjugation and Ligation DOI Creative Commons
Nikolaos Kaplaneris,

Alejandro Puet,

Felix Kallert

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(9)

Published: Dec. 30, 2022

Abstract Bioorthogonal late‐stage diversification of structurally complex peptides bears enormous potential for drug discovery and molecular imaging, among other applications. Herein, we report on a palladium‐catalyzed C−H arylation tryptophan‐containing with readily accessible modular arylthianthrenium salts. Under exceedingly mild reaction conditions, the was accomplished. The tunability ease preparation salts allowed expedient stitching drug, natural product, peptidic scaffolds by forging sterically congested biaryl linkages. robustness palladium catalysis regime reflected full tolerance plethora sensitive coordinating functional groups. Hence, our manifold enabled efficient access to highly decorated, labelled, conjugated, ligated linear cyclic peptides.

Language: Английский

Citations

45
Ruthenium‐Catalyzed Stereo‐ and Site‐Selective ortho‐ and meta‐C−H Glycosylation and Mechanistic Studies DOI

Xue‐Ya Gou,

Yuke Li,

Wei‐Yu Shi

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(32)

Published: June 8, 2022

Abstract C‐aryl glycosides are popular basic skeletons in biochemistry and pharmaceutical chemistry. Herein, ruthenium‐catalyzed highly stereo‐ site‐selective ortho ‐ meta ‐C Ar −H glycosylation is described. A series of pyranosides furanosides were synthesized by this method. The strategy showed good substrate scope, various N ‐heterocyclic directing groups compatible with the reaction system. mechanistic study suggested that key pathway might involve oxidative addition/reduction elimination, whereas aryl ‐C−H was mediated σ ‐activation. Density functional theory calculations also high stereoselectivity due to steric hindrance.

Language: Английский

Citations

44
Atropoenantioselective palladaelectro-catalyzed anilide C–H olefinations viable with natural sunlight as sustainable power source DOI Creative Commons
Johanna Frey, Xiaoyan Hou, Lutz Ackermann

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 13(9), P. 2729 - 2734

Published: Jan. 1, 2022

Asymmetric pallada-electrocatalyzed C–H activation of achiral anilides were accomplished by catalyst control with high levels enantioselectivity. Dual catalysis was devised, while photovoltaic cells could be used to empower the electrocatalysis.

Language: Английский

Citations

39
Stereoselective alkylC-glycosylation of glycosyl estersviaanomeric C–O bond homolysis: efficient access toC-glycosyl amino acids andC-glycosyl peptides DOI Creative Commons

Anrong Chen,

Shiyin Zhao,

Yang Han

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(27), P. 7569 - 7580

Published: Jan. 1, 2023

A novel photoredox-catalyzed radical conjugate addition of 1,4-dihydropyridine-derived glycosyl esters and dehydroalanine derivatives via anomeric C(sp 3 )–O bond homolysis to construct C -glycosyl amino acids peptides is for the first time described.

Language: Английский

Citations

33