Syntheses and chemical properties of β-nicotinamide riboside and its analogues and derivatives

• Mikhail V. Makarov and
• Marie E. Migaud

Beilstein J. Org. Chem. 2019, 15, 401–430, doi:10.3762/bjoc.15.36

Synthesis of nonracemic hydroxyglutamic acids

• Dorota G. Piotrowska,
• Iwona E. Głowacka,
• Andrzej E. Wróblewski and
• Liwia Lubowiecka

Beilstein J. Org. Chem. 2019, 15, 236–255, doi:10.3762/bjoc.15.22

• boron trifluoride-catalyzed reaction with trimethylsilyl cyanide were separated chromatographically. Their transformation into (2R,3S)-2 and (2S,3S)-2, respectively, required the removal of the p-methoxybenzyl group and an acidic hydrolysis (Scheme 14) [65]. From D-glucose D-Glucose may be used as a

• chiral template for the synthesis of (2S,3R)-2 since configurations at C3 and C4 in the hexose are retained in the target compound. The disclosed strategy relied on prior transformation of D-glucose into azidofuranoside 57 [66] and next to acid 58. Homologation of acid 58 was accomplished by the Arndt

• serine or their synthetic equivalents, glutamic acid, 4-hydroxyproline and pyroglutamic acid were most frequently employed. Alternatively, α-hydroxy acids (malic, tartaric) offered the opportunity to induce chirality at Cα–N while the stereochemistry at C–OH was retained. Monosaccharides (glucose, ribose

First synthesis of cryptands with sucrose scaffold

• Patrycja Sokołowska,
• Michał Kowalski and
• Sławomir Jarosz

Beilstein J. Org. Chem. 2019, 15, 210–217, doi:10.3762/bjoc.15.20

• sucrose scaffold (e.g., 4) can be also prepared successfully [15][16]. All macrocyclic derivatives, shown in Figure 1, were prepared from hexa-O-benzylsucrose 3 by a connection of the terminal positions of glucose (C6) and fructose (C6’) units. Results and Discussion Diol 3 may be also used as a starting

Unexpected loss of stereoselectivity in glycosylation reactions during the synthesis of chondroitin sulfate oligosaccharides

• Teresa Mena-Barragán,
• José L. de Paz and
• Pedro M. Nieto

Beilstein J. Org. Chem. 2019, 15, 137–144, doi:10.3762/bjoc.15.14

• oligosaccharides in order to improve the glycosylation efficiency [20][21]. In this approach, glucose instead of GlcA residues were employed in the oligosaccharide assembly and final oxidation and derivatization was carried out at the oligomer stage. Syndecan-1 glycopeptide containing a CS type A sequence was also

Adhesion, forces and the stability of interfaces

• Robin Guttmann,
• Johannes Hoja,
• Christoph Lechner,
• Reinhard J. Maurer and
• Alexander F. Sax

Beilstein J. Org. Chem. 2019, 15, 106–129, doi:10.3762/bjoc.15.12

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

• recognition. While manno- and glucopyranosides are also present in the eukaryotic glycocalyx, galactofuranosides, arabinofuranosides, and the (1→1)-linked glucose disaccharide trehalose are unique to the mycobacterial cell wall. The occurrence of galactose in the furanose form is restricted to bacteria [56

• . identified several monosaccharides able to disperse mycobacterial clumps and inhibit bacterial cellular aggregation when added to pure cultures, including D-arabinose (both M. smegmatis and Mtb), D-xylose, inositol, and D-glucose (M. smegmatis only). The impact of D-glucose on M. smegmatis aggregation was

Ruthenium-based olefin metathesis catalysts with monodentate unsymmetrical NHC ligands

• Veronica Paradiso,
• Chiara Costabile and
• Fabia Grisi

Beilstein J. Org. Chem. 2018, 14, 3122–3149, doi:10.3762/bjoc.14.292

• of highly performing NHC-based metathesis catalysts with N-alkyl groups, ruthenium benzylidene complexes containing carbohydrate-based NHCs derived from glucose (116) and galactose (117, Figure 21) were reported in 2009 [41]. These complexes were characterized in solution by NMR techniques which

A simple and effective preparation of quercetin pentamethyl ether from quercetin

• Jin Tatsuzaki,
• Tomohiko Ohwada,
• Yuko Otani,
• Reiko Inagi and
• Tsutomu Ishikawa

Beilstein J. Org. Chem. 2018, 14, 3112–3121, doi:10.3762/bjoc.14.291

• their broad spectrum of activities [2][3][4][5][6][7][8]. Kaempferia parviflora Wall. ex. Baker (Zingiberaceae), called “black turmeric” or “black ginger” in southern Asia, has been used as a folk medicine for vitality, as a nutritional supplement, and to reduce blood glucose levels; it has been

Repurposing the anticancer drug cisplatin with the aim of developing novel Pseudomonas aeruginosa infection control agents

• Mingjun Yuan,
• Song Lin Chua,
• Yang Liu,
• Daniela I. Drautz-Moses,
• Joey Kuok Hoong Yam,
• Thet Tun Aung,
• Roger W. Beuerman,
• May Margarette Santillan Salido,
• Stephan C. Schuster,
• Choon-Hong Tan,
• Michael Givskov,
• Liang Yang and
• Thomas E. Nielsen

Beilstein J. Org. Chem. 2018, 14, 3059–3069, doi:10.3762/bjoc.14.284

• glucose and 0.4 g/L casamino acids). For marker selection in P. aeruginosa, 30 μg mL−1 gentamycin (Gm), 50 μg mL−1 tetracycline (Tc), 100 μg mL−1 streptomycin (Strep) or 200 μg mL−1 carbenicillin (Cb) were used, as appropriate. Platinum complexes and solution preparation for MIC assay Cisplatin

Enhanced single-isomer separation and pseudoenantiomer resolution of new primary rim heterobifunctionalized α-cyclodextrin derivatives

• Iveta Tichá,
• Gábor Benkovics,
• Milo Malanga and
• Jindřich Jindřich

Beilstein J. Org. Chem. 2018, 14, 2829–2837, doi:10.3762/bjoc.14.261

• prepare these derivatives on α-, β- or γ-CDs, disubstitutions of the α-CD primary rim occurring at two different glucose units (Figure 1) stands out for well-explored direct and indirect approaches. The indirect preparation of selectively disubstituted CDs, including protecting and deprotecting steps, was

• the third (Mes-2) to methyl groups on the mesitylene skeleton (2.60–2.30 ppm). In the CD region, three areas are well distinguished – peaks about 5.07 ppm (CD H-1) belong to H-1 protons of four unsubstituted glucose units, whereas H-1 protons of glucoses with the azido moiety and the

• mesitylenesulfonyl moieties. Both substituents on the α-CD primary rim were also confirmed by HSQC in the anomeric region distinguished in three different parts. However, the crucial splitting of six C-1 anomeric doublets for the characterization of each glucose unit was not achieved. Overall, the two different

Impact of Pseudomonas aeruginosa quorum sensing signaling molecules on adhesion and inflammatory markers in endothelial cells

• Carmen Curutiu,
• Florin Iordache,
• Veronica Lazar,
• Aurelia Magdalena Pisoschi,
• Aneta Pop,
• Mariana Carmen Chifiriuc and
• Alina Maria Hoban

Beilstein J. Org. Chem. 2018, 14, 2580–2588, doi:10.3762/bjoc.14.235

• mutant strains initially form biofilms with the same dense structure as wild strains. The mutant strains produce even "mushroom"-like structures similar to wild strains that have as carbon source, glucose, but compared to wild type, mature biofilms (10 or more days of development) produced by QS

Functionalization of graphene: does the organic chemistry matter?

• Artur Kasprzak,
• Agnieszka Zuchowska and
• Magdalena Poplawska

Beilstein J. Org. Chem. 2018, 14, 2018–2026, doi:10.3762/bjoc.14.177

• and hydrogen bonding-dependent adsorption of glucose on the RGO surface results in a shift of the absorption bands coming from the C=O of RGO (from 1724 cm−1 to 1735 cm−1). Another consideration is that this process further influences the obtained material’s morphology, properties and thermal

Anomeric modification of carbohydrates using the Mitsunobu reaction

• Julia Hain,
• Patrick Rollin,
• Werner Klaffke and
• Thisbe K. Lindhorst

Beilstein J. Org. Chem. 2018, 14, 1619–1636, doi:10.3762/bjoc.14.138

• native D-glucose, D-GlcNAc or D-maltose resulted in regioselective esterification of the primary OH group, leaving all other hydroxy groups including the anomeric OH unmodified [38]. On the other hand, other authors have reported that the anomeric position can be selectively modified in a Mitsunobu

• -chloroacetyl-D-glucose (30) as well as its galacto-configured analogue with the carboxylic acids 31–34 to obtain products 35–38 which are related to various pesticide agents (Scheme 6). Their results supported the theory that, along with an effect of the reaction temperature, an increase of the pKa of the

• reaction, leading to aryl glycosides with reducing sugars as the alcohol components. Grynkiewicz can be called the pioneer of Mitsunobu glycosylation, as having explored the Mitsunobu reaction for the synthesis of various aryl glycosides [24][45]. Thus, native sugars such as D-glucose and D-mannose (Scheme

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

• yields for the one-pot process are comparable or superior to those obtained with the two-step procedure (Scheme 18). Synthesis of disaccharides Classically, carbohydrates have been considered primarily an energy source for life – as in the cases of glucose, fructose and their oligosaccharides, e.g

Lanyamycin, a macrolide antibiotic from Sorangium cellulosum, strain Soce 481 (Myxobacteria)

• Lucky S. Mulwa,
• Rolf Jansen,
• Dimas F. Praditya,
• Kathrin I. Mohr,
• Patrick W. Okanya,
• Joachim Wink,
• Eike Steinmann and
• Marc Stadler

Beilstein J. Org. Chem. 2018, 14, 1554–1562, doi:10.3762/bjoc.14.132

• , strain Soce 481, was isolated in 1990 from a soil sample with plant residue collected at Alanya in Turkey in 1986 and stored at −80 °C. It was reactivated in 20 mL of liquid medium composed of 0.1% soya meal, 0.15% casitone, 0.1% yeast extracts, 0.1% CaCl2, 50 mM HEPES (11.9 g), 0.1% glucose, 0.4% starch

• % glucose, 0.8% starch, 0.1% CaCl2, 0.1% MgSO4, 11.9% yeast extract, 1 mL/L Fe-EDTA, pH 7.4. Each flask was inoculated with 100 mL of well-grown 5-day culture, and then incubated in shake flask on a rotary shaker (160 rpm) at 25 °C for 14 days as recently described in [18]. Isolation of compounds 1 and 2

• extract, 0.1% yeast extract, pH 7.0) for bacteria and MYC medium (1.0% glucose, 1.0% phytone peptones, 50 mM HEPES (11.9 g/L), pH 7.0) for fungi as previously described [20]. 150 µL of the inoculated medium was dispensed in each well in 96-well microtiter plate. 20 µL and 2 µL aliquots of 1 mg/mL of test

Two new 2-alkylquinolones, inhibitory to the fish skin ulcer pathogen Tenacibaculum maritimum, produced by a rhizobacterium of the genus Burkholderia sp.

• Dandan Li,
• Naoya Oku,
• Atsumi Hasada,
• Masafumi Shimizu and
• Yasuhiro Igarashi

Beilstein J. Org. Chem. 2018, 14, 1446–1451, doi:10.3762/bjoc.14.122

• seed-cultured in 500 mL K-1 flasks each containing 100 mL of medium V-22 (soluble starch 1%, glucose 0.5%, NZ-case 0.3%, yeast extract 0.2%, tryptone 0.5%, K2HPO4 0.1%, MgSO4·7H2O 0.05%, and CaCO3 0.3%, pH 7.0) by rotary shaking at 200 rpm at 30 °C for two days. A three-mL aliquot of the resulting

• culture was inoculated into 100 mL of the IMM-HS production medium (glucose 1%, K2HPO4 0.36%, KH2PO4 0.41%, MgSO4·7H2O 0.02%, CaCl2·2H2O 0.01%, FeSO4·7H2O 0.002%, NH4Cl 0.1%, biotin 0.0001%, and L-histidine 0.4%), and shaken at 200 rpm at 30 °C for 4 days. For the extraction of secondary metabolites, 100

Synthetic avenues towards a tetrasaccharide related to Streptococcus pneumonia of serotype 6A

• Aritra Chaudhury,
• Mana Mohan Mukherjee and
• Rina Ghosh

Beilstein J. Org. Chem. 2018, 14, 1095–1102, doi:10.3762/bjoc.14.95

• bears a repeating unit, α-D-Galp(1->3)-α-D-Glcp(1->3)-α-L-Rhap(1->3)-D-Rib (SPn 6A). A closer look at the structure reveals the presence of α-linked galactose and glucose residues. The synthesis of these 1,2-cis glycosidic linkages are considered challenging particularly in the context of a one-pot

• conditions [41], followed by hydrogenation with H2/Pd-C in EtOH/EtOAc/AcOH solvent to give the deprotected tetrasaccharide 23 in 85% yield over two steps. 1H NMR in D2O of the target tetrasaccharide 23 showed the anomeric protons of the galactose, glucose, and rhamnose residues from the non-reducing end

An overview of recent advances in duplex DNA recognition by small molecules

• Sayantan Bhaduri,
• Nihar Ranjan and
• Dev P. Arya

Beilstein J. Org. Chem. 2018, 14, 1051–1086, doi:10.3762/bjoc.14.93

• conjugates in the minor groove by marinating a stable hairpin structure [96]. The authors tethered various monosaccharides such as β-xylose, α-xylose, β-galactose, β-glucose and β-L-fucose to a minor groove binding residue, Py-γ-Py-Ind, structurally analogous to distamycin and netropsin. A new set of novel

On the design principles of peptide–drug conjugates for targeted drug delivery to the malignant tumor site

• Eirinaios I. Vrettos,
• Gábor Mező and
• Andreas G. Tzakos

Beilstein J. Org. Chem. 2018, 14, 930–954, doi:10.3762/bjoc.14.80

• increased glucose uptake by cancer cells [12]. Nowadays, it has been demonstrated that malignant cells differ markedly in many metabolic aspects compared to normal cells [13], thus offering the opportunity to target them in various ways. Most cancer tissues exhibit the following characteristics that can be

Synthesis and in vitro biochemical evaluation of oxime bond-linked daunorubicin–GnRH-III conjugates developed for targeted drug delivery

• Sabine Schuster,
• Beáta Biri-Kovács,
• Bálint Szeder,
• Viktor Farkas,
• László Buday,
• Zsuzsanna Szabó,
• Gábor Halmos and
• Gábor Mező

Beilstein J. Org. Chem. 2018, 14, 756–771, doi:10.3762/bjoc.14.64

• times with serum-free medium and one time with HPMI medium (containing 100 mM NaCl, 5.4 mM KCl, 0.4 mM MgCl2, 0.04 mM CaCl2, 10 mM Hepes, 20 mM glucose, 24 mM NaHCO3 and 5 mM Na2HPO4 at pH 7.4) and trypsinized for 10 min at 37 °C. Trypsinization was stopped by HPMI medium supplemented with 10% FBS

Nanoreactors for green catalysis

• M. Teresa De Martino,
• Loai K. E. A. Abdelmohsen,
• Floris P. J. T. Rutjes and
• Jan C. M. van Hest

Beilstein J. Org. Chem. 2018, 14, 716–733, doi:10.3762/bjoc.14.61

• conversion of glucose in a tandem reaction [82]. The hydrophilic block of their polymersomes was PEG, and the hydrophobic block contained both poly[2-(diethylamino)ethyl methacrylate] (PDEAEM) which is pH responsive, and poly[4-(3,4-dimethylmaleimido)butyl methacrylate] (PDMIBM) as cross-linker. The activity

• of glucose oxidase (GOx) to convert glucose into D-glucono-δ-lactone and hydrogen peroxide was the first step of the reaction (Scheme 3A); subsequently, myoglobin (Myo) employed the hydrogen peroxide produced to oxidize guaiacol to quinone and water (Scheme 3B). When the pH was below 7, the

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

• good to excellent yields. Results and Discussion We began our studies by treating per-O-acetylated glucose with 3 equiv trimethylsilyl azide in the presence of 10 mol % AuBr3 in dichloromethane at room temperature. The reaction proceeded smoothly giving 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl azide

• , but the starting materials remained unaffected. Finally, the potential of the gold(III)-catalyzed azidation for large scale applications was demonstrated by performing a gram-scale synthesis on glucose peracetate giving product 2 in 90% yield. Conclusion In summary, a facile methodology demonstrating

• -acetylated glucose. Scope of AuBr3-catalyzed azido glycosylation of peracetates. Scope of AuBr3-catalyzed azido glycosylation of perbenzoylated sugars. Supporting Information Supporting Information File 70: Plausible catalytic cycle, experimental data and copies of 1H and 13C NMR spectra of glycosyl azides

Synthesis of a sucrose-based macrocycle with unsymmetrical monosaccharides "arms"

• Karolina Tiara,
• Mykhaylo A. Potopnyk and
• Sławomir Jarosz

Beilstein J. Org. Chem. 2018, 14, 634–641, doi:10.3762/bjoc.14.50

• functionalized sucrose amines of type 9 (Figure 2) which will be obtained by a selective introduction of different fragments 8 (obtained from, e.g., glucose, mannose, etc.). At this stage we were focused on the elaboration of a methodology allowing to introduce different fragments at the sucrose terminals. We

• of alcohol 13 (derived from D-glucose) with a rigid fragment and we decided to introduce the phenyl ring. Treatment of alcohol 13 with para-nitrophenol under Mitsunobu conditions afforded the nitro compound 14 in 63% yield. Stereoisomeric alditol 15, obtained from D-mannose, was converted analogously

Latest development in the synthesis of ursodeoxycholic acid (UDCA): a critical review

• Fabio Tonin and
• Isabel W. C. E. Arends

Beilstein J. Org. Chem. 2018, 14, 470–483, doi:10.3762/bjoc.14.33

• an immobilized NAD+-dependent 7α-HSHS (first reactor column); afterwards, 7-oxo-LCA is reduced to UDCA by an immobilized NADP+-dependent 7β-HSDH (second reactor column). The cofactors are individually regenerated in each column by the co-immobilized enzymes, lactate dehydrogenase (LDH) and glucose

• most used enzymes for the cofactor regeneration are glucose dehydrogenase (glucose to glucuronic acid), lactate dehydrogenase (pyruvate to lactate), glutamate dehydrogenase (α-ketoglutarate to glutamate) and formate dehydrogenase (formate to CO2). In particular, the last enzyme is interesting because

• (88.5 g L−1 d−1) for the epimerization of CDCA to UDCA. However, the employed enzymes have different cofactor specificities, leading to the consumption of stoichiometric amounts of sacrificial substrates (pyruvate and glucose). In addition, substrate loadings in the latter process are still modest (10

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

• was used by Wang for the more extended synthesis of a dodecasaccharide oxazoline (Scheme 6) [78]. In this case selective removal of the PMB protecting group at OH-3 was followed by glycosylation with a pentasaccharide glycosyl fluoride donor, comprising one galactose, one glucose, and three mannose