A selective and mild glycosylation method of natural phenolic alcohols

• Mária Mastihubová and
• Monika Poláková

Beilstein J. Org. Chem. 2016, 12, 524–530, doi:10.3762/bjoc.12.51

• acetylated glycosyl bromides 13, 15–20 derived from pyranoses, furanoses and a disaccharide (Figure 2) were prepared as glycosyl donors in one step and high yields starting from the peracetylated sugars. The glycosyl bromides depicted in Figure 2 were subsequently examined in the glycosylation of acceptors

Recent advances in N-heterocyclic carbene (NHC)-catalysed benzoin reactions

• Rajeev S. Menon,
• Akkattu T. Biju and
• Vijay Nair

Beilstein J. Org. Chem. 2016, 12, 444–461, doi:10.3762/bjoc.12.47

• influence of these catalysts on the diastereoselectivity of the reaction was also studied using NMR techniques. An NHC-catalysed intramolecular benzoin condensation of carbohydrate-derived dialdehydes has been applied for the construction of carbocyclic sugars. Diastereoselective benzoin reactions of manno

Self and directed assembly: people and molecules

• Tony D. James

Beilstein J. Org. Chem. 2016, 12, 391–405, doi:10.3762/bjoc.12.42

• group were developing carbohydrate receptors from what looked like simple molecules requiring just one or two steps to synthesize. Therefore, while working with the late Takaaki Harada, we developed a simple colorimetric system able to “read-out” the chirality of sugars. The system we developed used the

Mycothiol synthesis by an anomerization reaction through endocyclic cleavage

• Shino Manabe and
• Yukishige Ito

Beilstein J. Org. Chem. 2016, 12, 328–333, doi:10.3762/bjoc.12.35

• glycolipids [35][36][37]. Sulfated sugars are isomerized from pyranosides to furanosides [38]. The anomerization reaction would be a useful methodology to prepare 1,2-cis-glycosides such as heparin and glycosylphosphatidylinositol (GPI) anchors. Structure of mycothiol 1. Detoxification pathway mediated by MSH

Enabling technologies and green processes in cyclodextrin chemistry

• Giancarlo Cravotto,
• Marina Caporaso,
• Laszlo Jicsinszky and
• Katia Martina

Beilstein J. Org. Chem. 2016, 12, 278–294, doi:10.3762/bjoc.12.30

• and a high electrochemical response [74]. CuAAC has been successfully used to immobilize molecules on polymers and biopolymers as well as to join sugars to peptides and proteins. CD-polyglycerol dendron amphiphiles (CD-PG) have also been obtained. This derivative showed high encapsulation efficiency

Assembly of synthetic Aβ miniamyloids on polyol templates

• Sebastian Nils Fischer and
• Armin Geyer

Beilstein J. Org. Chem. 2015, 11, 2646–2653, doi:10.3762/bjoc.11.284

• molecular weights in the region of several kilodalton. Sugars (polyols) were already investigated as templates for peptides [6] and vice versa [7] but both concepts were not yet used for the assembly of monodisperse Aβ miniamyloids. Lehn’s concept of constitutional dynamic chemistry (CDC) [8][9] relies on

• precautions were necessary for peptides of type 2. The template should match the spacing of about 4 Å between the Aβ peptides within the Aβ fibrils [22]. Sugars appear as structurally diverse polyfunctional templates, but the problem of regioselective esterification is shown in Figure 3. The condensation of

Smart molecules for imaging, sensing and health (SMITH)

• Bradley D. Smith

Beilstein J. Org. Chem. 2015, 11, 2540–2548, doi:10.3762/bjoc.11.274

• inexperienced group, we started out looking at synthetic transport carriers for biomolecules such as sugars, nucleotides, amino acids, and catecholamines [5] (Scheme 2). Later on we started looking at chloride transport and we enjoyed a very productive collaboration with the British group of A. P. Davis to

Versatile synthesis and biological evaluation of novel 3’-fluorinated purine nucleosides

• Hang Ren,
• Haoyun An,
• Paul J. Hatala,
• William C. Stevens Jr,
• Jingchao Tao and
• Baicheng He

Beilstein J. Org. Chem. 2015, 11, 2509–2520, doi:10.3762/bjoc.11.272

• formation and ring opening as well as reversion of the hydroxy group on the sugar ring. Jeong and co-workers [38][39][40] synthesized fluorine-substituted ribofuranose but isolation required a challenging separation. Therefore, the synthetic challenges for preparing 3’-fluorine modified sugars and

Dicarboxylic esters: Useful tools for the biocatalyzed synthesis of hybrid compounds and polymers

• Ivan Bassanini,
• Karl Hult and
• Sergio Riva

Beilstein J. Org. Chem. 2015, 11, 1583–1595, doi:10.3762/bjoc.11.174

• esterifications of sugars and steroids, using acylating agents different from simple aliphatic acids [7][8][9]. Specifically, years ago Dordick and coworkers proposed the so-called ‘combinatorial biocatalysis’ as an approach to easily produce small libraries of derivatives of bioactive natural compounds using a

Structure and conformational analysis of spiroketals from 6-O-methyl-9(E)-hydroxyiminoerythronolide A

• Ana Čikoš,
• Irena Ćaleta,
• Dinko Žiher,
• Mark B. Vine,
• Ivaylo J. Elenkov,
• Marko Dukši,
• Dubravka Gembarovski,
• Marina Ilijaš,
• Snježana Dragojević,
• Ivica Malnar and
• Sulejman Alihodžić

Beilstein J. Org. Chem. 2015, 11, 1447–1457, doi:10.3762/bjoc.11.157

• ; spiroketal; Introduction Macrolide antibiotics are natural or semi-synthetic products of polyketide origin, containing one or more desoxy sugars attached to a macrocyclic lactone aglycon. This large and structurally diverse category of compounds has traditionally been divided into classes based on the

Are D-manno-configured Amadori products ligands of the bacterial lectin FimH?

• Tobias-Elias Gloe,
• Insa Stamer,
• Cornelia Hojnik,
• Tanja M. Wrodnigg and
• Thisbe K. Lindhorst

Beilstein J. Org. Chem. 2015, 11, 1096–1104, doi:10.3762/bjoc.11.123

• ligation method for conjugation of unprotected sugars and amines, when applied to suitable sugar substrates. Herein, we evaluated this synthetic method for the preparation of ligands for the α-D-mannose-specific type 1-fimbrial bacterial lectin FimH. The synthesis of heptopyranose 8 as a starting material

N-Alkyl derivatives of diosgenyl 2-amino-2-deoxy-β-D-glucopyranoside; synthesis and antimicrobial activity

• Agata Walczewska,
• Daria Grzywacz,
• Dorota Bednarczyk,
• Małgorzata Dawgul,
• Andrzej Nowacki,
• Wojciech Kamysz,
• Beata Liberek and
• Henryk Myszka

Beilstein J. Org. Chem. 2015, 11, 869–874, doi:10.3762/bjoc.11.97

• diosgenin. Very often this D-glucopyranose is substituted with α-L-rhamnopyranose at 2-OH and other sugars at 4-OH. The change of D-glucopyranose into 2-amino-2-deoxy-D-glucopyranose provides diosgenyl 2-amino-2-deoxy-β-D-glucopyranoside (7), a synthetic saponin, first reported by us [39]. It was also

• summarized and presented. We have studied different glycosyl donors, different amine group protections, different solvents and promoters to find the best way to obtain 7. The presented compilation is informative for all those interested in the glycosidation of 2-amino-2-deoxy sugars. Results and Discussion

Peptide–polymer ligands for a tandem WW-domain, an adaptive multivalent protein–protein interaction: lessons on the thermodynamic fitness of flexible ligands

• Katharina Koschek,
• Vedat Durmaz,
• Oxana Krylova,
• Marek Wieczorek,
• Shilpi Gupta,
• Martin Richter,
• Alexander Bujotzek,
• Christina Fischer,
• Rainer Haag,
• Christian Freund,
• Marcus Weber and
• Jörg Rademann

Beilstein J. Org. Chem. 2015, 11, 837–847, doi:10.3762/bjoc.11.93

• with an average MW of either 10 kDa (for Dex-1 and Dex-2) or 50 kDa (for Dex-3), both with a polydispersity index of 1.5. Under basic conditions the linear polysaccharide was alkylated with acrylamide selectively in the 2-positions of the sugars. The resulting 2-O-carboxyethyl dextran (2-O-CE-dextran

Orthogonal dual-modification of proteins for the engineering of multivalent protein scaffolds

• Michaela Mühlberg,
• Michael G. Hoesl,
• Christian Kuehne,
• Jens Dernedde,
• Nediljko Budisa and
• Christian P. R. Hackenberger

Beilstein J. Org. Chem. 2015, 11, 784–791, doi:10.3762/bjoc.11.88

• galactose 2 (see Supporting Information File 1). Lower concentrations of CuSO4 led to higher degrees of functionalization with 3–4 (10 mol %, Gal-3) galactose units, whereas higher amounts of Cu2+ led to lower degrees of functionalization with 1–2 clicked sugars (30 mol %, Gal-1). Further evidence for

Probing multivalency in ligand–receptor-mediated adhesion of soft, biomimetic interfaces

• Stephan Schmidt,
• Hanqing Wang,
• Daniel Pussak,
• Simone Mosca and
• Laura Hartmann

Beilstein J. Org. Chem. 2015, 11, 720–729, doi:10.3762/bjoc.11.82

• generally low affinity between sugars and receptors and possibly also by the high flexibility of the polymeric mannose linkers [9]. High molecular flexibility causes a high degree of conformational entropy that negatively affects complex formation between ligands and receptors [23]. Also the design of the

Synthesis of 1,2-cis-2-C-branched aryl-C-glucosides via desulfurization of carbohydrate based hemithioacetals

• Henok H. Kinfe,
• Fanuel M. Mebrahtu,
• Mandlenkosi M. Manana,
• Kagiso Madumo and
• Mokela S. Sokamisa

Beilstein J. Org. Chem. 2015, 11, 583–588, doi:10.3762/bjoc.11.64

• defensive low molecular weight thiol [7]. 2-C-acetamide and 2-C-acetonyl carbohydrate derivatives have also been reported to serve as inhibitors of the biosynthesis of lipids [8][9] and cell surface engineering [10], respectively. The main synthetic protocols for the synthesis of 2-C-branched sugars involve

• the regioselective ring opening of 1,2-cyclopropanated carbohydrates and the radical addition reaction of glycals [11][12][13][14][15]. Although the synthetic methodologies developed for the synthesis of C-glycosides and 2-C-branched sugars are extensively studied, the synthesis of 1,2-cis-2-C

• starting material. Compared to the previously reported protocols, especially via opening of 1,2-cyclopropanated sugars [30][31], the current strategy is superior in stereoselectivity and amenability of the 2-C-branch for further manipulation. The synthetic application of the 2-carbaldehyde of the aryl-C

3α,5α-Cyclocholestan-6β-yl ethers as donors of the cholesterol moiety for the electrochemical synthesis of cholesterol glycoconjugates

• Aneta M. Tomkiel,
• Adam Biedrzycki,
• Jolanta Płoszyńska,
• Dorota Naróg,
• Andrzej Sobkowiak and
• Jacek W. Morzycki

Beilstein J. Org. Chem. 2015, 11, 162–168, doi:10.3762/bjoc.11.16

• leads to sterol glycoconjugates. Initially, the reaction of cholesterol (1) with various sugars was studied. During anodic oxidation of cholesterol in dichloromethane (the choice of solvent is crucial as the reaction course may be different in other solvents) [1], splitting of the carbon–oxygen bond in

Release of β-galactosidase from poloxamine/α-cyclodextrin hydrogels

• César A. Estévez,
• José Ramón Isasi,
• Eneko Larrañeta and
• Itziar Vélaz

Beilstein J. Org. Chem. 2014, 10, 3127–3135, doi:10.3762/bjoc.10.330

• group. When the galactosyl acceptor is water, a galactose molecule is produced and the hydrolysis of lactose occurs. However, this transfer can be performed onto other acceptors such as sugars, yielding oligosaccharides through a transglycosylation mechanism [5]. Hydrogels are 3D networks capable of

Enantioselective synthesis of polyhydroxyindolizidinone and quinolizidinone derivatives from a common precursor

• Nemai Saha and
• Shital K. Chattopadhyay

Beilstein J. Org. Chem. 2014, 10, 3104–3110, doi:10.3762/bjoc.10.327

• complement to those existing in the literature. The prepared compounds may also prove to be biologically important. Selected polyhydroxyindolizidine and quinolizidines of importance. Target bicyclic imino sugars Ia and Ib from a common intermediate IV. Selected nOe correlations (A) and coupling constants (B

Synthesis of divalent ligands of β-thio- and β-N-galactopyranosides and related lactosides and their evaluation as substrates and inhibitors of Trypanosoma cruzi trans-sialidase

• María Emilia Cano,
• Rosalía Agusti,
• Alejandro J. Cagnoni,
• María Florencia Tesoriero,
• José Kovensky,
• María Laura Uhrig and
• Rosa M. de Lederkremer

Beilstein J. Org. Chem. 2014, 10, 3073–3086, doi:10.3762/bjoc.10.324

• [32][33]. In the present work, we selected thioglycosidic and N-glycosidic bonds to link the acceptor sugars to a platform by click chemistry, taking into consideration that they are highly resistant to enzymatic hydrolysis [34][35]. We have previously described the synthesis of multivalent β

Preparation and evaluation of cyclodextrin polypseudorotaxane with PEGylated liposome as a sustained release drug carrier

• Kayoko Hayashida,
• Taishi Higashi,
• Daichi Kono,
• Keiichi Motoyama,
• Koki Wada and
• Hidetoshi Arima

Beilstein J. Org. Chem. 2014, 10, 2756–2764, doi:10.3762/bjoc.10.292

• various targeting-ligands such as antibodies, sugars and folic acid to LPs [30][31][32]. Recently, stimulus responsive LPs such as bubble LPs, pH responsive LPs and thermoresponsive LPs have been developed as smart drug carriers [33][34][35]. PEGylated LP (PEG-LP) is one of the most popular LP products

Gold(I)-catalysed synthesis of a furan analogue of thiamine pyrophosphate

• Amjid Iqbal,
• El-Habib Sahraoui and
• Finian J. Leeper

Beilstein J. Org. Chem. 2014, 10, 2580–2585, doi:10.3762/bjoc.10.270

• ., pyruvate dehydrogenase, pyruvate decarboxylase), the formation of amino acid precursors (acetohydroxy acid synthase), and ketol transfer between sugars (transketolase) [1]. One common feature of ThDP-dependent enzymes is to catalyse the cleavage and formation of bonds adjacent to the carbon of a carbonyl

Synthesis of aromatic glycoconjugates. Building blocks for the construction of combinatorial glycopeptide libraries

• Markus Nörrlinger and
• Thomas Ziegler

Beilstein J. Org. Chem. 2014, 10, 2453–2460, doi:10.3762/bjoc.10.256

• Markus Norrlinger Thomas Ziegler Institute of Organic Chemistry, University of Tuebingen, Auf der Morgenstelle 18, 72076 Tuebingen, Germany 10.3762/bjoc.10.256 Abstract New aromatic glycoconjugate building blocks based on the trifunctional 3-aminomethyl-5-aminobenzoic acid backbone and sugars

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

• . In this way, almost quantitative recovery of the activated sugars 11–13 was achieved. Active esters 11–13 were then coupled with the amino groups of the protein in sodium phosphate buffer (100 mM NaPi, pH 7.2) at room temperature for 24 h (Scheme 3). The glycoconjugates 14–16 were purified from the

• latter analytical technique enabled determination of the saccharide/protein molar ratio (saccharide loading). The characteristics of the prepared glycoconjugates are summarized in Table 1. A moderate loading (5–7 sugars/protein) was obtained in compounds 14–16 in respect to conjugates prepared by the

Multivalent glycosystems for nanoscience

• Thisbe K. Lindhorst

Beilstein J. Org. Chem. 2014, 10, 2345–2347, doi:10.3762/bjoc.10.244

• this field of research. Now, a third “sweet” Thematic Series is presented in which the borderline between Alice’s Wonderland and real-life applications of carbohydrates has been deliberately crossed. The structural world of natural sugars has been extended towards artificial carbohydrate architectures