Comparison of glycosyl donors: a supramer approach

• Anna V. Orlova,
• Nelly N. Malysheva,
• Maria V. Panova,
• Nikita M. Podvalnyy,
• Michael G. Medvedev and
• Leonid O. Kononov

Beilstein J. Org. Chem. 2024, 20, 181–192, doi:10.3762/bjoc.20.18

• and straightforward as it is usually considered. Keywords: concentration; glycosylation; protecting groups; reactivity; sialic acids; stereoselectivity; Introduction Glycoconjugates containing sialic acid occur on the surface of all cell types in a variety of organisms. They participate in a broad

Synthesis of the 3’-O-sulfated TF antigen with a TEG-N₃ linker for glycodendrimersomes preparation to study lectin binding

• Mark Reihill,
• Hanyue Ma,
• Dennis Bengtsson and
• Stefan Oscarson

Beilstein J. Org. Chem. 2024, 20, 173–180, doi:10.3762/bjoc.20.17

• electrospray ionisation (ESI) in positive mode. MALDI–TOF mass spectrometry data were recorded on a Scientific Analysis Instruments MALDI–TOF mass spectrometer in reflectron mode for oligosaccharides and in linear mode for glycoconjugates. Samples were prepared by pre-mixing 1 µL of a solution containing the

Anomeric 1,2,3-triazole-linked sialic acid derivatives show selective inhibition towards a bacterial neuraminidase over a trypanosome trans-sialidase

• Peterson de Andrade,
• Sanaz Ahmadipour and
• Robert A. Field

Beilstein J. Org. Chem. 2022, 18, 208–216, doi:10.3762/bjoc.18.24

• typically found as a terminal unit of surface glycoconjugates and is crucial to various cellular recognition events in both physiological and pathological processes [1]. This distinctive negatively charged monosaccharide is the natural substrate for sialidases, which belong to different glycoside hydrolase

• acid from the human host glycoconjugates onto its surface mucins to generate α-2,3-linked sialylated β-galactopyranose units, thus contributing directly to the parasite adhesion and invasion of host cells [12]. Although TcTS is the major parasite virulence factor [13], there is no nanomolar inhibitor

Total synthesis of the O-antigen repeating unit of Providencia stuartii O49 serotype through linear and one-pot assemblies

• Tanmoy Halder and
• Somnath Yadav

Beilstein J. Org. Chem. 2021, 17, 2915–2921, doi:10.3762/bjoc.17.199

• development [1][2][3][4][5][6][7][8]. This objective has been proposed to be achieved by the synthesis of chemically homogeneous glycoconjugates bearing the O-antigen oligosaccharide conjugated to peptides for eliciting the desired immune response through vaccines [9][10][11][12][13][14][15][16][17][18][19

Metal-free glycosylation with glycosyl fluorides in liquid SO₂

• Krista Gulbe,
• Jevgeņija Lugiņina,
• Edijs Jansons,
• Artis Kinens and
• Māris Turks

Beilstein J. Org. Chem. 2021, 17, 964–976, doi:10.3762/bjoc.17.78

• glycoconjugates [1][2][3][4]. Due to the large diversity of glycosyl donors and acceptors there is no general glycosylation method developed so far. To ensure high yielding, as well as regio- and stereoselective glycosidic bond formation, a proper combination of glycosyl donor and acceptor, protecting and leaving

A consensus-based and readable extension of Linear Code for Reaction Rules (LiCoRR)

• Benjamin P. Kellman,
• Yujie Zhang,
• Emma Logomasini,
• Eric Meinhardt,
• Karla P. Godinez-Macias,
• Austin W. T. Chiang,
• James T. Sorrentino,
• Chenguang Liang,
• Bokan Bao,
• Yusen Zhou,
• Sachiko Akase,
• Isami Sogabe,
• Thukaa Kouka,
• Elizabeth A. Winzeler,
• Iain B. H. Wilson,
• Matthew P. Campbell,
• Sriram Neelamegham,
• Frederick J. Krambeck,
• Kiyoko F. Aoki-Kinoshita and
• Nathan E. Lewis

Beilstein J. Org. Chem. 2020, 16, 2645–2662, doi:10.3762/bjoc.16.215

• . Krambeck Kiyoko F. Aoki-Kinoshita Nathan E. Lewis See end of main text. 10.3762/bjoc.16.215 Abstract Systems glycobiology aims to provide models and analysis tools that account for the biosynthesis, regulation, and interactions with glycoconjugates. To facilitate these methods, there is a need for a

• illustrations, Linear Code described a simplified version of IUPAC nomenclature [31]. Specifically, Linear Code is a syntax for representing glycoconjugates and their associated molecules in a simple linear fashion. While keeping the linkage and branch information, Linear Code removes the hyphens between

Computational tools for drawing, building and displaying carbohydrates: a visual guide

• Kanhaya Lal,
• Rafael Bermeo and
• Serge Perez

Beilstein J. Org. Chem. 2020, 16, 2448–2468, doi:10.3762/bjoc.16.199

• glycoconjugates, which helps the communication of structure details within the scientific community. We highlight the comparative analysis of the available tools which could help researchers to perform various tasks related to structure representation and model building of glycans. These tools can be useful for

• together either linearly or branched); (ii) polysaccharides (for glycan chains composed of more than ten monosaccharides); (iii) glycoconjugates (where the glycan chains are covalently linked to proteins (glycoproteins), lipids (glycolipids). The complexity of glycans is a consequence of their branched

• program for sketching, building and 3D structure analysis of glycans and glycoconjugates. The scope of this work is relevant to N- and O-linked glycans, glycolipids, proteoglycans and glycosaminoglycans, lipopolysaccharides, plant, algal and bacterial polysaccharides. Review Methods To facilitate

Tools for generating and analyzing glycan microarray data

• Akul Y. Mehta,
• Jamie Heimburg-Molinaro and
• Richard D. Cummings

Beilstein J. Org. Chem. 2020, 16, 2260–2271, doi:10.3762/bjoc.16.187

• utilizes a different mechanism of binding the ligands to the surface. Choosing an appropriate surface often depends on the type of glycoconjugates to be printed, as well as the GBP and detection wavelengths used. For example, a nitrocellulose surface has an intrinsic high background when scanned at 488 nm

• monitoring for accurate printing. Between the printing of each probe (glycan), there is usually a wash step which is performed to prevent any carryover for the next ligand, and this would need to be determined empirically depending on the glycoconjugates used. After the entire print run, the slides are left

• synthesized, or isolated and purified from either source materials, and then conjugated with a linker which is appropriate for the printing surface. The glycoconjugates are then printed upon appropriately functionalized slides, followed by blocking; the printed slides are stored under ideal conditions prior

Synthesis of monophosphorylated lipid A precursors using 2-naphthylmethyl ether as a protecting group

• Jundi Xue,
• Ziyi Han,
• Gen Li,
• Khalisha A. Emmanuel,
• Cynthia L. McManus,
• Qiang Sui,
• Dongmian Ge,
• Qi Gao and
• Li Cai

Beilstein J. Org. Chem. 2020, 16, 1955–1962, doi:10.3762/bjoc.16.162

• ; lipid X; lipopolysaccharide; 2-naphthylmethyl ether; synthesis; Introduction Bacterial cell surfaces are decorated with various types of glycoconjugates (in the form of glycoproteins and glycolipids) that are known to participate in many biological processes, especially in the interactions between

• functionalities in target molecules for the synthesis of glycoconjugates. Based on the synthetic strategy described in this work (a common building block and Nap ether protection), we have already designed a route to MPLA, a clinically safe [30] monophosphoryl lipid A derivative with one phosphate group linked to

Synthesis of new asparagine-based glycopeptides for future scanning tunneling microscopy investigations

• Laura Sršan and
• Thomas Ziegler

Beilstein J. Org. Chem. 2020, 16, 888–894, doi:10.3762/bjoc.16.80

• the synthesis of structurally defined peptidomimetic libraries for further biological and medicinal investigation [4][8]. Recently, the characterization of heterogeneous mixtures of glycoconjugates was simplified by the development of novel MS-supported methods [9][10][11]. Nevertheless, the

• the aromatic backbone and known interaction of the compounds with Cu(100) and Au(111), ʟ-Phe and ʟ-Trp should be distinguishable in STM from the remaining building blocks [16][18][21]. ʟ-Ala seemed to be an ideal supplement for the synthesis of these new glycoconjugates since there was no additional

SnCl₄-catalyzed solvent-free acetolysis of 2,7-anhydrosialic acid derivatives

• Kesatebrhan Haile Asressu and
• Cheng-Chung Wang

Beilstein J. Org. Chem. 2019, 15, 2990–2999, doi:10.3762/bjoc.15.295

• University, Hsinchu 300, Taiwan 10.3762/bjoc.15.295 Abstract Sialic acid-containing glycans are found in different sialic acid forms and a variety of glycosidic linkages in biologically active glycoconjugates. Hence, the preparation of suitably protected sialyl building blocks requires high attention in

• ]. N-Acetylneuraminic acid (Neu5Ac) is the most studied monosaccharide from the 50 derivatives of sialic acid that are found in nature. The most common glycosidic linkages of Neu5Ac in glycoconjugates are α(2→3) and α(2→6) to galactose, α(2→8) and α(2→9) in polysialic acids [2][3], fucosyl and

Regioselectivity of glycosylation reactions of galactose acceptors: an experimental and theoretical study

• Enrique A. Del Vigo,
• Carlos A. Stortz and
• Carla Marino

Beilstein J. Org. Chem. 2019, 15, 2982–2989, doi:10.3762/bjoc.15.294

• carbohydrates in living systems, oligosaccharides and other glycoconjugates are needed to carry out the corresponding glycobiological studies. The heterogeneity of carbohydrates from natural sources makes their isolation difficult, which results in synthesis being the best alternative to obtain the required

• with more than one free hydroxy group allows reducing the usage of protecting groups, and thus developing simpler reaction sequences for the synthesis of oligosaccharides and glycoconjugates. A current alternative is the use of biocatalysts [4][5], although limited specific enzymes are available

• supported by theoretical studies [10][11]. ᴅ-Galactose (ᴅ-Gal) is one of the most abundant sugars in nature and a component of oligosaccharides and glycoconjugates with relevant functions [12]. Following a methodology previously applied to ᴅ-glucosamine acceptors [8] with some modifications, in the present

Towards the preparation of synthetic outer membrane vesicle models with micromolar affinity to wheat germ agglutinin using a dialkyl thioglycoside

• Dimitri Fayolle,
• Nathalie Berthet,
• Bastien Doumeche,
• Olivier Renaudet,
• Peter Strazewski and
• Michele Fiore

Beilstein J. Org. Chem. 2019, 15, 937–946, doi:10.3762/bjoc.15.90

• ]. GVs were prepared by hydrating a thin film containing 90:10 (mol %) of those glycoconjugates in mixture with a natural phospholipid: 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC). As expected, the mixture once hydrated showed a high tendency to vesiculate (Figure 3, images a–e and h

• compounds similar to other efficient multivalent glycoconjugates obtained by TEC of sugar thiols with different multivalent scaffolds such as octasilsesquioxanes [35], cyclopeptides [36][37] and polymers [38]. Both compounds 5 and 8 showed low IC50 values (a tenth to some hundreds of micromolars) where the

Design and synthesis of multivalent α-1,2-trimannose-linked bioerodible microparticles for applications in immune response studies of Leishmania major infection

• Chelsea L. Rintelmann,
• Tara Grinnage-Pulley,
• Kathleen Ross,
• Daniel E. K. Kabotso,
• Angela Toepp,
• Anne Cowell,
• Christine Petersen,
• Balaji Narasimhan and
• Nicola Pohl

Beilstein J. Org. Chem. 2019, 15, 623–632, doi:10.3762/bjoc.15.58

• system recognizes parasite surface glycoconjugates, or pathogen-associated molecular patterns (PAMPs), to build an immune response against the parasite and impede disease progression. Antigen presenting cells (APCs) recognize these PAMPs as pathogenic as compared to host glycans making these moieties

• feasible targets for both parasite detection and vaccine development [3]. Leishmania, an obligate intracellular parasite with varying surface glycoconjugates, infects an estimated 12 million people worldwide and has 350 million people at risk in endemic areas (predominately in underdeveloped countries

• intracellular pathogens, such as Mycobacterium tuberculosis [10][11]. Carbohydrate-based probes provide one method to investigate parasitic mechanisms of immune suppression and evasion. The cell surface glycoconjugates on Leishmania have been implicated in the ability of the parasite to infect host cells, then

Cyclopropene derivatives of aminosugars for metabolic glycoengineering

• Jessica Hassenrück and
• Valentin Wittmann

Beilstein J. Org. Chem. 2019, 15, 584–601, doi:10.3762/bjoc.15.54

• Diels–Alder reaction; metabolic engineering; Introduction Carbohydrates are an important class of biological molecules involved in many fundamental biological processes [1]. An important tool to visualize glycoconjugates in vitro and in vivo is metabolic glycoengineering (MGE) [2][3][4]. In this

• approach, cells are cultivated with an unnatural carbohydrate derivative carrying a chemical reporter group. After cellular uptake, the derivative is deacetylated, metabolized by the biosynthetic machinery and incorporated into glycoconjugates. The chemical reporter group can then be visualized using a

• membrane glycoconjugates. However, many processes are responsible for the staining intensity of either intracellular or cell-surface proteins including cellular uptake of the carbohydrate derivative used for MGE, its metabolization, transport, speed of the ligation reaction, and the occurrence of

Low-budget 3D-printed equipment for continuous flow reactions

• Jochen M. Neumaier,
• Amiera Madani,
• Thomas Klein and
• Thomas Ziegler

Beilstein J. Org. Chem. 2019, 15, 558–566, doi:10.3762/bjoc.15.50

• shows a good resistance towards common solvents. A disadvantage of FDM is the relatively low resolution [20]. Oligosaccharides, especially as glycoconjugates, play a crucial biological role in nature, e.g., for signal transduction in cell–cell recognition, infection processes, and immunology [21][22

• applicability of our flow system for such reactions. For studying biological interactions of saccharides and glycoconjugates it is crucial to chemically synthesize such compounds since material isolated from natural sources is often insufficiently pure. In such syntheses, the glycosylation step is usually the

Convergent synthesis of the pentasaccharide repeating unit of the biofilms produced by Klebsiella pneumoniae

• Arin Gucchait,
• Angana Ghosh and
• Anup Kumar Misra

Beilstein J. Org. Chem. 2019, 15, 431–436, doi:10.3762/bjoc.15.37

• contrast to the natural version. The synthesized molecules can be linked with appropriate functionalities for their conjugation with a protein for the preparation of glycoconjugates. Recently, Cescutti et al. [11] reported the structure of a pentasaccharide composed of D-glucose, D-mannose and D-glucuronic

Lectins of Mycobacterium tuberculosis – rarely studied proteins

• Katharina Kolbe,
• Sri Kumar Veleti,
• Norbert Reiling and
• Thisbe K. Lindhorst

Beilstein J. Org. Chem. 2019, 15, 1–15, doi:10.3762/bjoc.15.1

• cells exhibit a diverse array of glycoconjugates on their cell surfaces, together known as the glycocalyx (Figure 2). Carbohydrate moieties of the eukaryotic glycocalyx mainly exist in the form of oligosaccharide chains covalently linked to proteins or lipids. The most prevalent oligosaccharide

• biophysical and biochemical methods the domain structure of HBHA has been determined, and includes a canonical lysine-rich C-terminal heparin binding domain (see Figure 5) [83][102][103][104][105], which has been shown to bind sulfated glycoconjugates like heparin, facilitating the adhesion of mycobacteria to

Synthesis of α-D-GalpN₃-(1-3)-D-GalpN₃: α- and 3-O-selectivity using 3,4-diol acceptors

• Emil Glibstrup and
• Christian Marcus Pedersen

Beilstein J. Org. Chem. 2018, 14, 2805–2811, doi:10.3762/bjoc.14.258

• and present in several distinct entities. One of the most studied glycoconjugates, containing this sequence, is the Forssman antigen, in which this disaccharide is the terminal unit. The many biological roles attributed to this particular glycoconjugate and its appearance in some human tumors [1][2

Pathoblockers or antivirulence drugs as a new option for the treatment of bacterial infections

• Matthew B. Calvert,
• Varsha R. Jumde and
• Alexander Titz

Beilstein J. Org. Chem. 2018, 14, 2607–2617, doi:10.3762/bjoc.14.239

• pathogen [10]. 3. Blocking adhesion and biofilm formation Bacterial adhesion to the host’s tissue is the initial step of every infection. In many cases, microbial adhesion is mediated by carbohydrate-binding proteins, so-called lectins, which recognize glycoconjugates on the surface of cells and tissue

• . Surface exposed glycoconjugates are highly abundant on all living cells and are generally referred to as the glycocalyx. Bacterial lectins act as adhesins with defined carbohydrate-binding specificities, in order to establish and maintain infection of the host’s various tissues and organs. Therefore, the

Glycosylation reactions mediated by hypervalent iodine: application to the synthesis of nucleosides and carbohydrates

• Yuichi Yoshimura,
• Hideaki Wakamatsu,
• Yoshihiro Natori,
• Yukako Saito and
• Noriaki Minakawa

Beilstein J. Org. Chem. 2018, 14, 1595–1618, doi:10.3762/bjoc.14.137

• ., starch. However, more recently it has been revealed that oligosaccharides and glycoconjugates also play important roles in various biological processes, as mentioned earlier. As a result, the increasing significance of oligosaccharides in biological events has led to a strong demand for synthetic routes

• oxidative glycosylation reaction to stereoselectively give C2-acyloxylated β-glycosides in good yields [84] (Scheme 22). Hotha and co-workers utilized the reaction of glycals with hypervalent iodine reagents for the stereoselective synthesis of C2 deoxyglycosides and amino acid glycoconjugates [85]. In

• nucleoside derivatives. In addition to nucleoside synthesis, hypervalent iodine-mediated glycosylation could also be applied to the synthesis of oligosaccharides and glycoconjugates when thioglycosides and glycals were used as sugar donors. There is no doubt that the use of hypervalent iodine reagents

AuBr₃-catalyzed azidation of per-O-acetylated and per-O-benzoylated sugars

• Jayashree Rajput,
• Srinivas Hotha and
• Madhuri Vangala

Beilstein J. Org. Chem. 2018, 14, 682–687, doi:10.3762/bjoc.14.56

• ], glycoconjugates [30][31][32], N-glycosyl heterocycles [33][34], N-glycosyl triazole [35][36], etc. Glycosyl azides can be accessed from the corresponding glycosyl halides [37][38][39][40] by nucleophilic displacement with NaN3 or using trimethylsilyl azide in the presence of a phase transfer catalyst [41][42][43

• the ability of Au(III) in catalyzing the azidation of deactivated sugars was shown. The reaction proceeds in the absence of molecular sieves without forming lactols as byproducts. This operationally simple protocol enables the synthesis of various N-glycoconjugates offering a wide range of

Synthetic and semi-synthetic approaches to unprotected N-glycan oxazolines

• Antony J. Fairbanks

Beilstein J. Org. Chem. 2018, 14, 416–429, doi:10.3762/bjoc.14.30

• egg yolks, and also extended the variety of structures available by such means. It seems likely that more N-glycans will become available by such methods in the future. Furthermore it also appears to be only a matter of time until homogeneous glycoproteins and other glycoconjugates produced using N

Photocatalytic formation of carbon–sulfur bonds

• Alexander Wimmer and
• Burkhard König

Beilstein J. Org. Chem. 2018, 14, 54–83, doi:10.3762/bjoc.14.4

• linear and branched primary, secondary and aromatic thiols react with linear and substituted aliphatic alkenes and styrenes. Due to the high functional group tolerance, they demonstrated the applicability to the preparation of glycoconjugates from glycosyl thiols and amino acid derivatives. They propose

Aminosugar-based immunomodulator lipid A: synthetic approaches

• Alla Zamyatina

Beilstein J. Org. Chem. 2018, 14, 25–53, doi:10.3762/bjoc.14.3

• -hydrophobic labeling reagents for amphiphilic glycoconjugates such as lipid A. 1.4. Synthesis of Helicobacter pylori Kdo-lipid A substructures A Helicobacter pylori infection of the gastric mucosa causes chronic gastritis in humans and plays a pivotal role in the progression and pathogenesis of peptic ulcer