Silver Oxide Promoted Synthesis of Alpha O-GalNAc Containing Glyco-Amino Acids: Synthesis of Core 2 Containing Glyco-Amino Acids for Solid Phase Synthesis of Glycopeptides DOI

Olivier Boyé,

Lawrence W. Nicholson,

Anna Marstall

и другие.

The Journal of Organic Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Дек. 12, 2024

O-GalNAc glycans on glycoproteins with eight different core structures sharing a common α-glycosidic linkage (O-GalNAc-α-Ser/Thr) are critical in various physiological and pathological processes. Among the glycan cores, 2 characterized by GlcNAcβ1–6(Galβ1–3)GalNAc structural motif plays significant role regulating diverse biological processes, such as immune response modulation, adhesive properties of selectins, gastrointestinal tract protection. However, large-quantity synthesis containing glyco-amino acids for downstream solid-phase peptide is challenging. In this work, we successfully employed silver oxide coupling 2-azido-galactosyl chloride donor two acceptors, Fmoc-Ser/Thr-OtBu, respectively, large-scale important intermediates, α-GalN3–Fmoc-Ser/Thr-OtBu, which can be further utilized acids. The were synthesizing Fmoc-Ser/Thr-COOH. Fmoc-Ser-COOH was achieved 1.95 g scale, while Fmoc-Thr-COOH 0.38 scale. Additionally, optimized into three-step process only one column chromatography purification. Finally, Fmoc-Ser/Thr-COOH applied glycosylated CCR1 CCR5 N-terminal peptides.

Язык: Английский

Total Synthesis of Nona-decasaccharide Motif from Ganoderma sinense Polysaccharide Enabled by Modular and One-Pot Stereoselective Glycosylation Strategy DOI
Zhiyuan Chen, Guozhi Xiao

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(25), С. 17446 - 17455

Опубликована: Июнь 11, 2024

Polysaccharides from a medicinal fungus Ganoderma sinense represent important and adjunctive therapeutic agents for treating various diseases, including leucopenia hematopoietic injury. However, the synthetic accessibility to long, branched, complicated carbohydrates chains polysaccharides remains challenging task in chemical synthesis. Here, we report modular synthesis of nona-decasaccharide motif polysaccharide GSPB70-S with diverse biological activities first time through one-pot stereoselective glycosylation strategy on basis glycosyl ortho-(1-phenyvinyl)benzoates, which not only sped up but also reduced waste avoided aglycones transfer issues inherent thioglycosides. The route highlights following key steps: (1) preactivation-based highly constructions several 1,2-cis-glycosidic linkages, three α-d-GlcN-(1 → 4) linkages one α-d-Gal-(1 bond via reagent N-methyl-N-phenylformamide modulation; (2) orthogonal assembly 1,2-trans-glycosidic linear branched glycans fragments by strategic combinations N-phenyltrifluoroacetimidates, ortho-alkynylbenzoates, ortho-(1-phenyvinyl)benzoates; (3) final [1 × 4 + 15] Yu efficient target. Additionally, shorter sequences 4-mer, 5-mer, 6-mer are prepared structure–activity relationship studies. present work shows that this can offer reliable effective means streamline complex many bonds.

Язык: Английский

Процитировано

9
Total Synthesis of the Repeating Units of Highly Functionalized O-Antigens of Pseudomonas aeruginosa ATCC 27577, O10, and O19 DOI Creative Commons
Xiaoyu Yang, Han Zhang,

Qingpeng Zhao

и другие.

JACS Au, Год журнала: 2024, Номер 4(6), С. 2351 - 2362

Опубликована: Июнь 7, 2024

The first total synthesis of the repeating units O-antigens Pseudomonas aeruginosa ATCC 27577, O10, and O19 was achieved via a linear glycosylation strategy. This also represents an oligosaccharide containing α-linked N-acetyl-l-galactosaminuronic acid (l-GalpNAcA) unit. All glycosyl linkages, including three challenging 1,2-cis-glycosidic bonds amino sugars, were effectively constructed with high to exclusive stereoselectivity, while orthogonal protection tactics employed facilitate regioselective glycosylations introduction variety functionalities. An acetyl group migration phenomenon found during O-acylated unit P. 27577 antigen. synthetic targets carried functional in linker at reducing end, thus facilitating further elaboration biological studies. strategy established here should be useful for preparation other similar oligosaccharides.

Язык: Английский

Процитировано

4
Stereoselective Glycosylation for 1,2-cis-Aminoglycoside Assembly by Cooperative Atom Transfer Catalysis DOI
Hongze Li,

Zhang Da-kang,

Chong Li

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 25, 2024

We report here a new catalytic method for exclusively 1,2-

Язык: Английский

Процитировано

3
Stereoselective Multigram-Scale Tn Antigen Synthesis via the Iron-Catalyzed Glycal 1,2-cis-Aminoglycosylation DOI Creative Commons

Le Bin Yin,

Zhang Da-kang,

Zhonghao Jiang

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Май 16, 2025

We report here a new catalytic and exclusively cis-selective glycosylation strategy for multigram scale synthesis of biologically valuable Tn antigens. The underlying iron-catalyzed glycal 1,2-cis-aminoglycosylation method is effective with variety galactosyl donors amino acid acceptors consistently high stereoselectivity. Rapid scalable postglycosylation transformations readily afford single diastereomeric antigens in yields.

Язык: Английский

Процитировано

0
One-Pot Assembly of Octasaccharide Motif from Cranberry Arabinoxyloglucan Oligosaccharides DOI
Guozhi Xiao, Jie Wan

Synlett, Год журнала: 2024, Номер unknown

Опубликована: Июнь 30, 2024

Abstract Chemical synthesis of octasaccharide motif from cranberry arabinoxyloglucan oligosaccharides with antiadhesion activities has been achieved for the first time. Synthetic approach highlights following features: 1) stereoselective constructions 1,2-cis-Xyl bonds via combination reagent modulation and remote participation; 2) modular [1+3+1+3] orthogonal one-pot assembly target on basis glycosyl ortho-(1-phenylvinyl)benzoate, which avoids issues such as aglycone transfer associated glycosylation based thioglycosides.

Язык: Английский

Процитировано

0
ZnI2-Mediated cis-Glycosylations of Various Constrained Glycosyl Donors: Recent Advances in cis-Selective Glycosylations DOI Creative Commons
Akihiro Ishiwata,

Xuemei Zhong,

Katsunori Tanaka

и другие.

Molecules, Год журнала: 2024, Номер 29(19), С. 4710 - 4710

Опубликована: Окт. 4, 2024

An efficient and versatile glycosylation methodology is crucial for the systematic synthesis of oligosaccharides glycoconjugates. A direct intermolecular an indirect intramolecular have been developed, former can be applied to medium-to-long-chain glycans like that nucleotides peptides. The development a generally applicable approach stereoselective construction glycosidic bonds remains major challenge, especially 1,2-

Язык: Английский

Процитировано

0
Chemical synthesis of rhynchosporosides DOI
Xiufang Wang, Guozhi Xiao

Journal of Carbohydrate Chemistry, Год журнала: 2024, Номер unknown, С. 1 - 10

Опубликована: Окт. 11, 2024

Chemical synthesis of rhynchosporosides that cause scald diseases in barley has been summarized this review. The features two different strategies, namely, two-stage activation and one-pot glycosylation. Comparing with the stepwise synthesis, assembly strategy based on glycosyl ortho-(1-phenylvinyl)benzoates can highly streamline carbohydrates avoiding such problems as aglycone transfer associated traditional glycosylation thioglycosides.

Язык: Английский

Процитировано

0
Silver Oxide Promoted Synthesis of Alpha O-GalNAc Containing Glyco-Amino Acids: Synthesis of Core 2 Containing Glyco-Amino Acids for Solid Phase Synthesis of Glycopeptides DOI

Olivier Boyé,

Lawrence W. Nicholson,

Anna Marstall

и другие.

The Journal of Organic Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Дек. 12, 2024

O-GalNAc glycans on glycoproteins with eight different core structures sharing a common α-glycosidic linkage (O-GalNAc-α-Ser/Thr) are critical in various physiological and pathological processes. Among the glycan cores, 2 characterized by GlcNAcβ1–6(Galβ1–3)GalNAc structural motif plays significant role regulating diverse biological processes, such as immune response modulation, adhesive properties of selectins, gastrointestinal tract protection. However, large-quantity synthesis containing glyco-amino acids for downstream solid-phase peptide is challenging. In this work, we successfully employed silver oxide coupling 2-azido-galactosyl chloride donor two acceptors, Fmoc-Ser/Thr-OtBu, respectively, large-scale important intermediates, α-GalN3–Fmoc-Ser/Thr-OtBu, which can be further utilized acids. The were synthesizing Fmoc-Ser/Thr-COOH. Fmoc-Ser-COOH was achieved 1.95 g scale, while Fmoc-Thr-COOH 0.38 scale. Additionally, optimized into three-step process only one column chromatography purification. Finally, Fmoc-Ser/Thr-COOH applied glycosylated CCR1 CCR5 N-terminal peptides.

Язык: Английский

Процитировано

0