Synthesis and immunological evaluation of protein conjugates of Neisseria meningitidis X capsular polysaccharide fragments

• Laura Morelli,
• Damiano Cancogni,
• Marta Tontini,
• Alberto Nilo,
• Sara Filippini,
• Paolo Costantino,
• Maria Rosaria Romano,
• Francesco Berti,
• Roberto Adamo and
• Luigi Lay

Beilstein J. Org. Chem. 2014, 10, 2367–2376, doi:10.3762/bjoc.10.247

• be the result of a better exposition of monosaccharide and disaccharide MenX units in the context of the trimer-HSA molecule, due presumably to conformational or spatial factors. However, this peculiar recognition was not observed when the native MenX CPS, which is the structure that best resembles

Expanding the scope of cyclopropene reporters for the detection of metabolically engineered glycoproteins by Diels–Alder reactions

• Anne-Katrin Späte,
• Verena F. Schart,
• Julia Häfner,
• Andrea Niederwieser,
• Thomas U. Mayer and
• Valentin Wittmann

Beilstein J. Org. Chem. 2014, 10, 2235–2242, doi:10.3762/bjoc.10.232

• naturally biotinylated proteins. Principle of MOE with Ac4GlcNCyoc (1) and subsequent ligation by a DAinv reaction: The chemically modified sugar is fed to cells, taken up by the cells and deacetylated by non-specific esterases. The monosaccharide is metabolized and incorporated into glycoproteins (i.e., O

Indium-mediated allylation in carbohydrate synthesis: A short and efficient approach towards higher 2-acetamido-2-deoxy sugars

• Christopher Albler,
• Ralph Hollaus,
• Hanspeter Kählig and
• Walther Schmid

Beilstein J. Org. Chem. 2014, 10, 2230–2234, doi:10.3762/bjoc.10.231

• -configurated pyranose derivatives are known to adopt multiple conformations [32][33][34]. We were able to isolate and fully assign four distinct forms of the acetylated monosaccharide derivative 7a (β-furanoid, 4C1 α/β-pyranoid and 1C4 α-pyranoid). Although 7a is a known compound [15], the published NMR data

De novo macrolide–glycolipid macrolactone hybrids: Synthesis, structure and antibiotic activity of carbohydrate-fused macrocycles

• Richard T. Desmond,
• Anniefer N. Magpusao,
• Chris Lorenc,
• Jeremy B. Alverson,
• Nigel Priestley and
• Mark W. Peczuh

Beilstein J. Org. Chem. 2014, 10, 2215–2221, doi:10.3762/bjoc.10.229

• of the monosaccharide. The new macrocycles/macrolides were characterized by X-ray crystallography. Their structures showed that, in addition to the ester and alkene units, the dihedral angle about the glycosidic linkage (exo-anomeric effect) influenced the overall shape of the molecules

• ]. Conclusion We have described the synthesis and characterization of de novo macrolide 16 as a member of a family of related macrocyles that fuse a pyranose monosaccharide to the macrocyclic ring. The new compounds showed modest antibacterial activity against Gram positive organisms. The main conclusion of the

Why a diaminopyrrolic tripodal receptor binds mannosides in acetonitrile but not in water?

• Diogo Vila-Viçosa,
• Oscar Francesconi and
• Miguel Machuqueiro

Beilstein J. Org. Chem. 2014, 10, 1513–1523, doi:10.3762/bjoc.10.156

• over the years [1][2][3][4][5][6]. Most of these were developed for glucose since it is one of the most common sugars in living systems [7] and the preferred monosaccharide for energy storage [8]. However, mannose is essential for various biological functions, such as molecular recognition, being one

Multichromophoric sugar for fluorescence photoswitching

• Stéphane Maisonneuve,
• Rémi Métivier,
• Pei Yu,
• Keitaro Nakatani and
• Juan Xie

Beilstein J. Org. Chem. 2014, 10, 1471–1481, doi:10.3762/bjoc.10.151

• photo resistance. Keywords: click chemistry; energy transfer; fluorophore; monosaccharide; photochromism; Introduction The development of functional nanomaterials is nowadays a very attractive field of fundamental and applied research. The chemical functions at the molecular level yield properties

Carbohydrate PEGylation, an approach to improve pharmacological potency

• M. Eugenia Giorgi,
• Rosalía Agusti and
• Rosa M. de Lederkremer

Beilstein J. Org. Chem. 2014, 10, 1433–1444, doi:10.3762/bjoc.10.147

• is transferred to the glycan by a sialyltransferase. The serine or threonine residues in the O-glycosylation sites serve as acceptors for GalNAc using a convenient GalNAc transferase. This unit can be galactosylated by a galactosyltransferase and both, the monosaccharide and the disaccharide, may be

Human dendritic cell activation induced by a permannosylated dendron containing an antigenic GM₃-lactone mimetic

• Renato Ribeiro-Viana,
• Elena Bonechi,
• Javier Rojo,
• Clara Ballerini,
• Giuseppina Comito,
• Barbara Richichi and
• Cristina Nativi

Beilstein J. Org. Chem. 2014, 10, 1317–1324, doi:10.3762/bjoc.10.133

• mannose for DC targeting and one residue of the mimetic 3 as a carbohydrate melanoma-associated antigen. We have previously demonstrated that a glycodendron bearing nine copies of the monosaccharide mannose can be taken up by DCs in a receptor-dependent manner by means of the lectin DC-SIGN [34]. This

Synthesis of a sucrose dimer with enone tether; a study on its functionalization

• Zbigniew Pakulski,
• Norbert Gajda,
• Magdalena Jawiczuk,
• Jadwiga Frelek,
• Piotr Cmoch and
• Sławomir Jarosz

Beilstein J. Org. Chem. 2014, 10, 1246–1254, doi:10.3762/bjoc.10.124

• shown in Figure 2. The properly activated sugar is converted into phosphorane or phosphonate which – upon reaction with an aldehyde derived from another monosaccharide – provides higher carbon sugar (HCS) enone [16][17][18]. Application of this methodology to selectively protected 2,3,3’,4,4’-penta-O

Atherton–Todd reaction: mechanism, scope and applications

• Stéphanie S. Le Corre,
• Mathieu Berchel,
• Hélène Couthon-Gourvès,
• Jean-Pierre Haelters and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2014, 10, 1166–1196, doi:10.3762/bjoc.10.117

Convergent synthesis of a tetrasaccharide repeating unit of the O-specific polysaccharide from the cell wall lipopolysaccharide of Azospirillum brasilense strain Sp7

• Pintu Kumar Mandal,
• Debashis Dhara and
• Anup Kumar Misra

Beilstein J. Org. Chem. 2014, 10, 293–299, doi:10.3762/bjoc.10.26

• protected monosaccharide intermediates in 42% overall yield in seven steps by using a [2 + 2] block glycosylation approach. Keywords: Azospirillum brasilense; glycosylation; lipopolysaccharide; plant growth-promoting bacteria (PGPB); tetrasaccharide; Introduction The intensive use of chemicals for the

• 1. A number of suitably functionalized monosaccharide intermediates 2, 3 [30], 4 [31], and 5 [32] were prepared from the reducing sugars by using literature reports. The application of a one-pot reaction sequence for the stereoselective glycosylation and the removal of the p-methoxybenzyl (PMB

Stereoselectively fluorinated N-heterocycles: a brief survey

• Xiang-Guo Hu and
• Luke Hunter

Beilstein J. Org. Chem. 2013, 9, 2696–2708, doi:10.3762/bjoc.9.306

• as polyhydroxylated alkaloids or azasugars, are sugar mimics in which a nitrogen atom replaces the ring oxygen of the corresponding monosaccharide (Figure 8) [31][32][33][34][35][36]. Iminosugars can competitively bind to glycosidase enzymes because of their structural resemblance to the terminal

Biosynthesis of rare hexoses using microorganisms and related enzymes

• Zijie Li,
• Yahui Gao,
• Hideki Nakanishi,
• Xiaodong Gao and
• Li Cai

Beilstein J. Org. Chem. 2013, 9, 2434–2445, doi:10.3762/bjoc.9.281

• monosaccharides and their derivatives that rarely exist in nature (http://isrs.kagawa-u.ac.jp/activities.html) [1]. Seeberger et al. did some interesting statistical research on bacterial and mammalian glycomes, with one emphasis placed on the abundance of monosaccharide units (most abundant monosaccharides are

• as rare sugars due to their low abundance in nature. In addition, 1-deoxy-L-fructose is also a very rare but important monosaccharide [8]. The biosynthesis of these rare ketohexoses using microorganisms and related enzymes is summarized below. D-Tagatose D-Tagatose is a keto-/aldo-isomer of D

• monosaccharide for their growth. L-Glucose L-Glucose does not occur naturally in higher living organisms, although it has many potential applications, such as a low calorie sweetener [77], a bulking agent [78], an inhibitor for bacterial growth [79] and various glucosidases. L-Glucose can also be used as an

Synthesis of enantiopure sugar-decorated six-armed triptycene derivatives

• Paola Bonaccorsi,
• Maria Luisa Di Gioia,
• Antonella Leggio,
• Lucio Minuti,
• Teresa Papalia,
• Carlo Siciliano,
• Andrea Temperini and
• Anna Barattucci

Beilstein J. Org. Chem. 2013, 9, 2410–2416, doi:10.3762/bjoc.9.278

• Messina, Italy Dipartimento di Chimica e Tecnologia del Farmaco, Università di Perugia, via del Liceo 1, 06123 Perugia, Italy 10.3762/bjoc.9.278 Abstract A new class of molecules with a triptycene rigid core surrounded by six monosaccharide residues was synthesized. Hexakis(bromomethyl) substituted

Synthesis of mucin-type O-glycan probes as aminopropyl glycosides

• David Benito-Alifonso,
• Rachel A. Jones,
• Anh-Tuan Tran,
• Hannah Woodward,
• Nichola Smith and
• M. Carmen Galan

Beilstein J. Org. Chem. 2013, 9, 1867–1872, doi:10.3762/bjoc.9.218

• -galactopyranose monosaccharide and the side-chain hydroxy groups. Herein we report a convergent approach for the highly efficient synthesis of mucin type O-glycan fragments 1–7 (Figure 1) containing an α-linked 3-aminopropyl-spacer ready for covalent attachment to glycoarray platforms. Results and Discussion A

• % overall yield. The sequence involved temporary protection of the free hydroxy at C-3 by reaction with acetic anhydride and pyridine, SN2 displacement of the chloride in monosaccharide 9 with n-tetrabutylammonium iodide (n–TBAI) in refluxing acetonitrile followed by the addition of NaN3. Ester removal was

Straightforward synthesis of a tetrasaccharide repeating unit corresponding to the O-antigen of Escherichia coli O16

• Manas Jana and
• Anup Kumar Misra

Beilstein J. Org. Chem. 2013, 9, 1757–1762, doi:10.3762/bjoc.9.203

• presented herein (Figure 2). Results and Discussion The target tetrasaccharide as its p-methoxyphenyl (PMP) glycoside was synthesized following a sequential glycosylation approach from the suitably functionalized monosaccharide intermediates 2 [13], 3 [14], 4 [15] and 5 [16]. These monosaccharide

Short synthesis of the common trisaccharide core of kankanose and kankanoside isolated from Cistanche tubulosa

• Goutam Guchhait and
• Anup Kumar Misra

Beilstein J. Org. Chem. 2013, 9, 705–709, doi:10.3762/bjoc.9.80

• was synthesized from the suitably functionalized monosaccharide derivatives 2 [10], 3 [11], and 4 [12], which were prepared from the commercially available reducing sugars (Figure 1). The key features of this synthetic strategy are (a) the application of two regioselective glycosylations by using

De novo synthesis of D- and L-fucosamine containing disaccharides

• Daniele Leonori and
• Peter H. Seeberger

Beilstein J. Org. Chem. 2013, 9, 332–341, doi:10.3762/bjoc.9.38

• -Garner aldehydes. These differentially protected monosaccharide building blocks were utilized to prepare disaccharides present on the surface of Pseudomonas aeruginosa bacteria. Keywords: de novo synthesis; fucosamine; glycan; pseudomonas aeruginosa; vaccine; Introduction Protein functions are directly

• bacterium. In 2001, the P. aeruginosa pilin O-linked glycans were found to be linear trisaccharides that are covalently attached to serine (Figure 1). The O-glycans contain a D-fucosamine residue at the protein-binding site. This unusual monosaccharide is not present in eukaryotes, and therefore may be used

• activating agent, yielded the linker-functionalized monosaccharide D-12 as the β-anomer (3JH1–H2 = 8.3 Hz, Scheme 6A). At this point, the C3 naphthyl ether was cleaved under oxidative conditions and the corresponding alcohol was revealed by using a two-step deprotection protocol consisting of ester

Glycosylation efficiencies on different solid supports using a hydrogenolysis-labile linker

• Mayeul Collot,
• Steffen Eller,
• Markus Weishaupt and
• Peter H. Seeberger

Beilstein J. Org. Chem. 2013, 9, 97–105, doi:10.3762/bjoc.9.13

• /bjoc.9.13 Abstract Automated oligosaccharide assembly requires suitable linkers to connect the first monosaccharide to a solid support. A new hydrogenolysis-labile linker that is stable under both acidic and basic conditions was designed, synthesized and coupled to different resins. Glycosylation and

• avoid neutralization of the activator during glycosylation reactions, unreacted amino groups were capped by acetylation. Resin loadings with the amide-bound linkers 25–29 were determined by using variants including the ester insert for rapid cleavage (Table 1). Glycosylation with monosaccharide building

• hydrolyze the monosaccharide building blocks or may complex the acidic activators due to the presence of many Lewis basic sites on PEG chains [47]. Since the hydrogenolytic linker cleavage did not work equally well for all types of solid support, this cleavage method was ill suited for the comparison of

Removal of benzylidene acetal and benzyl ether in carbohydrate derivatives using triethylsilane and Pd/C

• Abhishek Santra,
• Tamashree Ghosh and
• Anup Kumar Misra

Beilstein J. Org. Chem. 2013, 9, 74–78, doi:10.3762/bjoc.9.9

• % yield in 30 min. Generalizing the reaction conditions, a series of benzylidene acetal containing monosaccharide and disaccharide derivatives, with different functional groups present in them, were treated with the optimized reagent system, and clean removal of benzylidene acetal was observed in all

Peptoids and polyamines going sweet: Modular synthesis of glycosylated peptoids and polyamines using click chemistry

• Daniel Fürniss,
• Timo Mack,
• Frank Hahn,
• Sidonie B. L. Vollrath,
• Katarzyna Koroniak,
• Ute Schepers and
• Stefan Bräse

Beilstein J. Org. Chem. 2013, 9, 56–63, doi:10.3762/bjoc.9.7

• solid phases [26][27][29][35][36][37][38][39]. However, the on-bead addition of oligosaccharide or monosaccharide modifications are not known so far. The modification of polyamines or peptoids is usually achieved by alternation of the termini [36][40] or by direct use of different side-chain

Synthesis of a derivative of α-D-Glcp(1->2)-D-Galf suitable for further glycosylation and of α-D-Glcp(1->2)-D-Gal, a disaccharide fragment obtained from varianose

• Carla Marino,
• Carlos Lima,
• Karina Mariño and
• Rosa M. de Lederkremer

Beilstein J. Org. Chem. 2012, 8, 2142–2148, doi:10.3762/bjoc.8.241

• disaccharide, were analysed by HPAEC–PAD (condition 1). A sample of this fraction was hydrolyzed with TFA 2 N, 105 °C, 3 h for total monosaccharide composition analysis by HPAEC–PAD (condition 2). HPAEC–PAD analysis Analysis by HPAEC–PAD was performed by using a Dionex ICS-3000 HPLC system equipped with a

Multivalent display of the antimicrobial peptides BP100 and BP143

• Imma Güell,
• Rafael Ferre,
• Kasper K. Sørensen,
• Esther Badosa,
• Iteng Ng-Choi,
• Emilio Montesinos,
• Eduard Bardají,
• Lidia Feliu,
• Knud J. Jensen and
• Marta Planas

Beilstein J. Org. Chem. 2012, 8, 2106–2117, doi:10.3762/bjoc.8.237

• -functionalized monosaccharide templates, such as cyclodithioerythritol (cDTE) or α-D-galactopyranoside (Galp) [23][26][27]. Here we describe the use of carbohydrate templates for the display of multiple copies of antimicrobial peptides. Our aim in this study was to evaluate whether the assembly of cecropin A

Convergent synthesis of the tetrasaccharide repeating unit of the cell wall lipopolysaccharide of Escherichia coli O40

• Abhijit Sau and
• Anup Kumar Misra

Beilstein J. Org. Chem. 2012, 8, 2053–2059, doi:10.3762/bjoc.8.230

• the suitably protected monosaccharide derivatives 2 [13], 3 [14], 4 [15] and 5 [16], which were prepared from the commercially available reducing sugars, by applying a series of functional group protection–deprotection methodologies (Figure 2). The synthetic strategy has a number of notable features

A new approach toward the total synthesis of (+)-batzellaside B

• Jolanta Wierzejska,
• Shin-ichi Motogoe,
• Yuto Makino,
• Tetsuya Sengoku,
• Masaki Takahashi and
• Hidemi Yoda

Beilstein J. Org. Chem. 2012, 8, 1831–1838, doi:10.3762/bjoc.8.210

• ; L-pyroglutamic acid; total synthesis; Introduction Iminosugars, monosaccharide analogues in which the endocyclic oxygen has been replaced by nitrogen, display beneficial therapeutic activity as sugar-mimicking glycosidase inhibitors [1][2][3][4]. Since the discovery of nojirimycin (Figure 1), which