The effect of neighbouring group participation and possible long range remote group participation in O-glycosylation

• Rituparna Das and
• Balaram Mukhopadhyay

Beilstein J. Org. Chem. 2025, 21, 369–406, doi:10.3762/bjoc.21.27

• multistep synthesis of complex oligosaccharides and in turn, standardise the process of the glycosylation towards a particular stereochemical output. While neighbouring group participation has been quite effective in achieving the required stereochemistry of the produced glycosides, remote participation

• it to obtain significant stereoselective glycosylation products in good yields. Acetyl and benzoyl protection: The total synthesis of oligosaccharides has seen numerous illustrations of the participating role of the acyl esters. Citing a few references in order to elaborate the mechanistic protocol

Synthesis of disulfides and 3-sulfenylchromones from sodium sulfinates catalyzed by TBAI

• Zhenlei Zhang,
• Ying Wang,
• Xingxing Pan,
• Manqi Zhang,
• Wei Zhao,
• Meng Li and
• Hao Zhang

Beilstein J. Org. Chem. 2025, 21, 253–261, doi:10.3762/bjoc.21.17

• -derived Functional Oligosaccharides Engineering Technology Research Center of Anhui Province, Fuyang Normal University, Fuyang, Anhui, 236037, P. R. China 10.3762/bjoc.21.17 Abstract A new synthetic method for disulfides and 3-sulfenylchromones is reported. This innovative approach is based on the

Computational toolbox for the analysis of protein–glycan interactions

• Ferran Nieto-Fabregat,
• Maria Pia Lenza,
• Angela Marseglia,
• Cristina Di Carluccio,
• Antonio Molinaro,
• Alba Silipo and
• Roberta Marchetti

Beilstein J. Org. Chem. 2024, 20, 2084–2107, doi:10.3762/bjoc.20.180

Polymer degrading marine Microbulbifer bacteria: an un(der)utilized source of chemical and biocatalytic novelty

• Weimao Zhong and
• Vinayak Agarwal

Beilstein J. Org. Chem. 2024, 20, 1635–1651, doi:10.3762/bjoc.20.146

• are glycoside hydrolases (GHs) that degrade agarose to smaller oligosaccharides [102]. Marine bacteria of diverse genera produce agarases [103][104][105]. Based on the reactions that they catalyze, bacterial agarases are grouped as α- and β-agarases wherein they hydrolyze α-1,3 linkages and β-1,4

• -reducing end of oligosaccharides. Based on their substrate specificity, β-glucosidases can be divided into aryl-β-glucosidases that act on aryl glucosides, cellobiases that hydrolyze the disaccharide cellobiose, and other glucosidases [122]. They can also be classified into GH-1 and GH-3 families based on

Photoswitchable glycoligands targeting Pseudomonas aeruginosa LecA

• Yu Fan,
• Ahmed El Rhaz,
• Stéphane Maisonneuve,
• Emilie Gillon,
• Maha Fatthalla,
• Franck Le Bideau,
• Guillaume Laurent,
• Samir Messaoudi,
• Anne Imberty and
• Juan Xie

Beilstein J. Org. Chem. 2024, 20, 1486–1496, doi:10.3762/bjoc.20.132

• bacterial infections occur by adhesion to host tissues through receptor–ligand interaction between bacterial carbohydrate-binding proteins (lectins) and oligosaccharides at the host cell surface. Pseudomonas aeruginosa (PA), a Gram-negative, opportunistic and ubiquitous environmental bacterium, is known as

Synthesis of cyclic β-1,6-oligosaccharides from glucosamine monomers by electrochemical polyglycosylation

• Md Azadur Rahman,
• Hirofumi Endo,
• Takashi Yamamoto,
• Shoma Okushiba,
• Norihiko Sasaki and
• Toshiki Nokami

Beilstein J. Org. Chem. 2024, 20, 1421–1427, doi:10.3762/bjoc.20.124

• protecting group afforded the cyclic disaccharide exclusively. Cyclic oligosaccharides up to the trisaccharide were obtained using the monomer with a 2-azido-2-deoxy group. Keywords: cyclic oligosaccharide; electrochemical glycosylation; glucosamine; polyglycosylation; Introduction Electrochemical

• reactions. Therefore, electrochemical polymerizations can be utilized for selective synthesis. Cyclic oligosaccharides are an important class of host molecules, and some natural cyclic oligosaccharides are produced by enzymatic processes. However, the corresponding chemical syntheses are still primitive [6

• ][7][8][9][10]. Thus, chemical glycosylation has to be improved to be able to synthesize complex oligosaccharides, including cyclic oligosaccharides. In this context, electrochemical glycosylation is an important alternative to conventional chemical glycosylations because the precise control of

Elucidating the glycan-binding specificity and structure of Cucumis melo agglutinin, a new R-type lectin

• Jon Lundstrøm,
• Emilie Gillon,
• Valérie Chazalet,
• Nicole Kerekes,
• Antonio Di Maio,
• Ten Feizi,
• Yan Liu,
• Annabelle Varrot and
• Daniel Bojar

Beilstein J. Org. Chem. 2024, 20, 306–320, doi:10.3762/bjoc.20.31

• , these substructures occurred in many different contexts, such as blood group H, LacdiNAc, or the Sda motif, and particularly in sequences resembling O-glycans, milk oligosaccharides, and glycosphingolipids. At first glance, these two binding specificities may seem unconnected, indicating a rather

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 conjugates are important for advancing glycobiology [12][13] and glyco-medicine [14][15]. However, the reliable installation of sialic acid residues in oligosaccharides is a rather difficult issue and poor predictability remains characteristic of the sialylation reaction [16][17][18][19][20][21

• donors that lead to formation of Neu-α(2-3)-Gal [33][34][37] and Neu-α(2-6)-Gal [32][34][36] glycosidic linkages found in oligosaccharides [59] of biological and medical significance. The supramer approach implies that changes in solute concentration can cause the supramers to rearrange and thus affect

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

GlAIcomics: a deep neural network classifier for spectroscopy-augmented mass spectrometric glycans data

• Thomas Barillot,
• Baptiste Schindler,
• Baptiste Moge,
• Elisa Fadda,
• Franck Lépine and
• Isabelle Compagnon

Beilstein J. Org. Chem. 2023, 19, 1825–1831, doi:10.3762/bjoc.19.134

• proposed to identify the presence of structural features in oligosaccharides based on their gas-phase IR spectra [11]. To the best of our knowledge, machine learning classification studies have not been reported to identify saccharides using MS–IR carbohydrate analysis. Here, we report a study of a

• oligosaccharides resulting from the fragmentation of a larger precursor possess a very specific IR fingerprint in the 2–4 microns spectral range, that is highly valuable to resolve all types of isomers [4]. Typical experimental IR fingerprint data are shown in Figure 1: they feature the intensities of the

Cyclodextrins permeabilize DPPC liposome membranes: a focus on cholesterol content, cyclodextrin type, and concentration

• Ghenwa Nasr,
• Hélène Greige-Gerges,
• Sophie Fourmentin,
• Abdelhamid Elaissari and
• Nathalie Khreich

Beilstein J. Org. Chem. 2023, 19, 1570–1579, doi:10.3762/bjoc.19.115

• content membrane increase. Keywords: cholesterol; cyclodextrins; liposome; membrane permeability; Introduction Cyclodextrins (CDs) are a family of cyclic oligosaccharides made of glucopyranose units connected by α-1,4-glycosidic bonds. They possess a cone-shaped molecular structure with a hydrophobic

CO₂ complexation with cyclodextrins

• Cecilie Høgfeldt Jessen,
• Jesper Bendix,
• Theis Brock Nannestad,
• Heloisa Bordallo,
• Martin Jæger Pedersen,
• Christian Marcus Pedersen and
• Mikael Bols

Beilstein J. Org. Chem. 2023, 19, 1021–1027, doi:10.3762/bjoc.19.78

• from industrial processes, power generation, and transportation contribute significantly to global warming and climate change. Carbon capture and storage (CCS) technologies are essential to reduce these emissions and mitigate the effects of climate change. Cyclodextrins (CDs), cyclic oligosaccharides

Continuous flow synthesis of 6-monoamino-6-monodeoxy-β-cyclodextrin

• János Máté Orosz,
• Dóra Ujj,
• Petr Kasal,
• Gábor Benkovics and
• Erika Bálint

Beilstein J. Org. Chem. 2023, 19, 294–302, doi:10.3762/bjoc.19.25

• ; monosubstitution; reduction; Introduction Cyclodextrins (CDs), as cyclic oligosaccharides, consist of a macrocyclic ring of glucose subunits linked by α-1,4-glycosidic bonds [1]. They are widely used in pharmaceutical, food and chemical industries, as well as in agriculture. It has been known for decades, that CD

Preparation of β-cyclodextrin/polysaccharide foams using saponin

• Max Petitjean and
• José Ramón Isasi

Beilstein J. Org. Chem. 2023, 19, 78–88, doi:10.3762/bjoc.19.7

• Max Petitjean Jose Ramon Isasi Department of Chemistry. University of Navarra. 31080 Pamplona, Spain 10.3762/bjoc.19.7 Abstract Cyclodextrins, cyclic oligosaccharides with a hydrophobic cavity that form inclusion complexes with nonpolar molecules, can be used to functionalize other

Inclusion complexes of the steroid hormones 17β-estradiol and progesterone with β- and γ-cyclodextrin hosts: syntheses, X-ray structures, thermal analyses and API solubility enhancements

• Alexios I. Vicatos,
• Zakiena Hoossen and
• Mino R. Caira

Beilstein J. Org. Chem. 2022, 18, 1749–1762, doi:10.3762/bjoc.18.184

• pharmaceutical industry for many decades. However, the complexation of APIs with cyclodextrins (cyclic oligosaccharides) resulting in the formation of inclusion complexes, has proven to be a versatile technology for overcoming not only the poor aqueous solubility of APIs, but also unfavourable properties such as

Cyclodextrin-based Schiff base pro-fragrances: Synthesis and release studies

• Attila Palágyi,
• Jindřich Jindřich,
• Juraj Dian and
• Sophie Fourmentin

Beilstein J. Org. Chem. 2022, 18, 1346–1354, doi:10.3762/bjoc.18.140

• molecules and protect those agents from environmental degradation [1][2]. Cyclodextrins (CDs) serve as one of the simplest encapsulating systems. CDs are cyclic oligosaccharides composed of 1→4 linked α-ᴅ-glucopyranose units (6, 7, and 8 for the most common α-, β-, and γ-CD). CDs are well known for their

Synthesis of protected precursors of chitin oligosaccharides by electrochemical polyglycosylation of thioglycosides

• Md Azadur Rahman,
• Kana Kuroda,
• Hirofumi Endo,
• Norihiko Sasaki,
• Tomoaki Hamada,
• Hiraku Sakai and
• Toshiki Nokami

Beilstein J. Org. Chem. 2022, 18, 1133–1139, doi:10.3762/bjoc.18.117

• Engineering, Tottori University, 4-101 Koyamacho-minami, Tottori City, 680-8552 Tottori, Japan Koganei Corporation, 3-11-28 Midorimachi, Koganei City, 184-8533 Tokyo, Japan 10.3762/bjoc.18.117 Abstract The synthesis of protected precursors of chitin oligosaccharides by electrochemical polyglycosylation of

• thioglycosides as monomer is described. Oligosaccharides up to the hexasaccharide were synthesized under optimized reaction conditions. Further, a modified method enabled the synthesis of oligosaccharides up to the octasaccharide by repeating electrolysis with additional monomers. The mechanism of the

• electrochemical polyglycosylation is also discussed, based on the oxidation potential of the monomer and oligosaccharides. Keywords: electrochemical glycosylation; glucosamine; oligosaccharide; oxidation potential; polyglycosylation; Introduction Chitin oligosaccharides are partial structures of chitin, which

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

• ][20][21]. For the above purposes, large scale access to pure, defined, and homogeneous samples of the desired LPS oligosaccharides are essential for realization of the goal towards vaccine development against these pathogens [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21

• % yield (Scheme 3). The linear synthesis of oligosaccharides is associated with several disadvantages such as multiple steps involving multiple work-up procedures, purifications requiring long time, manpower and the resulting high cost of synthesis and production. Consequently one-pot strategies have

Progress and challenges in the synthesis of sequence controlled polysaccharides

• Giulio Fittolani,
• Theodore Tyrikos-Ergas,
• Denisa Vargová,
• Manishkumar A. Chaube and
• Martina Delbianco

Beilstein J. Org. Chem. 2021, 17, 1981–2025, doi:10.3762/bjoc.17.129

• polymerization [18], C) chemical synthesis. The use of enzymes has undeniable advantages because it offers the possibility to use unprotected sugars as substrates and guarantees remarkable control of the regio- and stereoselectivity during glycosylation. Mono- or oligosaccharides bearing a reactive leaving group

• realized using a convergent approach [101]. The process was later simplified using AGA and several XG oligosaccharides were prepared [102]. Representative examples are 19 and 20 (Scheme 3) [103], as well as the galactose-containing compounds 21 and 22 [104]. These compounds permitted to study XG

• . Several oligosaccharides have been prepared to identify the best PG pattern ensuring a proper balance between BB reactivity, stereoselectivity, and simplicity of deprotection [113][114][115][116][117][118][119][120][121][122][123][124][125]. Ester groups are commonly employed at C-2 position to ensure

Chemical synthesis of C6-tetrazole ᴅ-mannose building blocks and access to a bioisostere of mannuronic acid 1-phosphate

• Eleni Dimitriou and
• Gavin J. Miller

Beilstein J. Org. Chem. 2021, 17, 1527–1532, doi:10.3762/bjoc.17.110

• this end, synthetic chemistry strategies (both solution and solid phase) have demonstrated exciting capabilities for access to native alginate oligosaccharides in recent years [6][7][8][9][10]. As part of a program to access non-native alginate oligosaccharide sequences, we targeted a synthetic

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

• oligosaccharides and glycopeptides under basic aqueous conditions [32][33]. Nevertheless, most of the conventional conditions for glycosyl fluoride activation have considerable drawbacks in terms of atom efficiency and environmental impact. These methods generally require (1) stoichiometric amounts of promoters

Leveraging glycomics data in glycoprotein 3D structure validation with Privateer

• Haroldas Bagdonas,
• Daniel Ungar and
• Jon Agirre

Beilstein J. Org. Chem. 2020, 16, 2523–2533, doi:10.3762/bjoc.16.204

• solve. Chiefly among these is the scenario where the experimentally resolved electron density map provides evidence of glycosylation, without enough resolution to derive definite and comprehensive details about the structural composition of the oligosaccharides (Figure 1). Glycan microheterogeneity and

• heterogeneous [22]. Moreover, oligosaccharides often significantly interfere with the formation of crystal contacts that allow the formation of well-diffracting crystals. Because of this, glycans are often truncated in MX samples to aid crystal formation [27]. In cryo-EM, samples of glycoproteins are vitrified

• glycoproteins [42]. The mass spectrometric analysis of glycosylated proteins can be with (glycomics) or without (glycoproteomics) the release of oligosaccharides from the glycoprotein. Usually, glycomics and glycoproteomics experiments are carried out together to obtain a complete description of the

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

• glucose. And yet, monosaccharides are only the chemical units and the individual building blocks of much more complex molecules; the carbohydrates, also referred to as glycans. The glycan family can be grouped in the following categories: (i) oligosaccharides (comprising two to ten monosaccharides linked

• of molecules; thus, it provides challenges in the development of force fields for accurate modelling of such variations in charge distributions. The monosaccharides can further form a large number of oligosaccharides which can enormously increase the conformational space, due to a high number of

• oligosaccharides containing additional groups like sulfates, phosphates etc. [24] Generally used force fields for the Molecular Mechanics (MD) simulation of carbohydrates are CHARMM [25], GLYCAM [26], and GROMOS [27]. The structural complexity increases the computational cost, which makes simulations of large

Synthesis of the tetrasaccharide repeating unit of the O-specific polysaccharide of Azospirillum doebereinerae type strain GSF71^T using linear and one-pot iterative glycosylations

• Arin Gucchait,
• Pradip Shit and
• Anup Kumar Misra

Beilstein J. Org. Chem. 2020, 16, 1700–1705, doi:10.3762/bjoc.16.141

• strategies could provide access to large quantities of the oligosaccharides with defined chemical structures and free from biological impurities. Among the nineteen species of Azospirillum, Azospirillum doebereinerae was isolated from the rhizosphere of the biomass producing plant, Miscanthus giganteus [20

Synthesis of Streptococcus pneumoniae serotype 9V oligosaccharide antigens

• Sharavathi G. Parameswarappa,
• Claney L. Pereira and
• Peter H. Seeberger

Beilstein J. Org. Chem. 2020, 16, 1693–1699, doi:10.3762/bjoc.16.140

• flexneri pentadecasaccharide that passed phase-I clinical trials [17][18] incorporate defined oligosaccharides. SP 9 contains four capsular types (9A, 9L, 9N and 9V) whereby the most prevalent, 9V (57%) affects young children and 9N (34%) infects adults [19]. CPS of 9V and 9A serotypes differ only in the