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

• 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

• structure. Up to date, only monosaccharides have been intensively used as chiral building blocks in the synthesis of such macrocycles. Less attention, however, has been paid to macrocycles with disaccharides (or oligosaccharides) being a part of the ring [6][7][8]. We have proposed to use sucrose (1) as a

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

• -acylated N-TFA-protected GalNAc donors and GlcA acceptors that is not due to the presence of the fluorous tail. We hypothesized that the substitution pattern of the GlcA acceptor was responsible for the displayed stereochemistry and some experiments with model monosaccharides were planned to confirm this

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

• . 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

Synthesis of 1,4-imino-L-lyxitols modified at C-5 and their evaluation as inhibitors of GH38 α-mannosidases

• Maroš Bella,
• Sergej Šesták,
• Ján Moncoľ,
• Miroslav Koóš and
• Monika Poláková

Beilstein J. Org. Chem. 2018, 14, 2156–2162, doi:10.3762/bjoc.14.189

• . Moreover, various desired substituents can be selectively appended to any required position of the carbohydrate unit. This leads to a preparation of mimetics that meet the requirements of metabolically more stable bioactive compounds. During the years, many scaffolds based on monosaccharides [4

• ], disaccharides or higher oligosaccharides [5][6] as well as multivalent [7][8] carbohydrate units have been developed. These glycomimetics and glycopeptides have also found applications as bioactive compounds [9][10]. One group of the scaffolds includes iminosugars [11][12] as analogues of the monosaccharides

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

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

• catalytic amounts of oxophilic AuBr3 in good to excellent yields. The method is applicable to a wide range of easily accessible per-O-acetylated and per-O-benzoylated sugars. While reaction with per-O-acetylated and per-O-benzoylated monosaccharides was complete within 1–3 h at room temperature, the per-O

• slow anomerization [52]. In 2011, Chen’s group reported that 5 mol % FeCl3 can catalyze the reaction of trimethylsilyl azide with per-O-acetylated β-monosaccharides to afford glycosyl azides in 3–7 h, whereas per-O-acetylated β-di- and trisaccharides required 22–28 h for complete conversion [53

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

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

• enzymes has therefore become an area of significant interest over the past 15 years [35][36]. The synthesis of N-glycan oxazolines Formation of glycosyl oxazolines Glycosyl oxazolines of monosaccharides can be produced straightforwardly using strong Lewis acids (e.g., FeCl3, SnCl4, or TMSOTf) and a fully

An efficient synthesis of a C₁₂-higher sugar aminoalditol

• Łukasz Szyszka,
• Anna Osuch-Kwiatkowska,
• Mykhaylo A. Potopnyk and
• Sławomir Jarosz

Beilstein J. Org. Chem. 2017, 13, 2146–2152, doi:10.3762/bjoc.13.213

• the coupling of two simple monosaccharides and subsequent transformation of the resulting enone into the protected C12-sugar 1. The conversion of the latter into alditol 2 allowed us to prepare derivative 3 having a 18-membered ring (Figure 1) [8]. Higher sugar 1 has a substantial synthetic potential

1,3-Dibromo-5,5-dimethylhydantoin as promoter for glycosylations using thioglycosides

• Fei-Fei Xu,
• Claney L. Pereira and
• Peter H. Seeberger

Beilstein J. Org. Chem. 2017, 13, 1994–1998, doi:10.3762/bjoc.13.195

• group at C-6 and C-4 position, respectively. The DBDMH/TfOH system activates glycosyl donors including neutral monosaccharides of different configurations (D-gluco 5 and 6, D-galacto 1 and 4, D-manno 8, L-rhamno 9), amino sugar 7 and uronic acid 10. All thioglycosides reacted equally well, irrespective

New bio-nanocomposites based on iron oxides and polysaccharides applied to oxidation and alkylation reactions

• Daily Rodríguez-Padrón,
• Alina M. Balu,
• Antonio A. Romero and
• Rafael Luque

Beilstein J. Org. Chem. 2017, 13, 1982–1993, doi:10.3762/bjoc.13.194

• nanocomposites with diverse applications in catalysis, sensing, drug delivery and adsorption [25][26][27][28]. In addition, mechanochemical protocols have also been employed to functionalize the surfaces of magnetic nanoparticles (MNPs) with monosaccharides [29] and to obtain bio-nanocomposites based on proteins

The chemistry and biology of mycolactones

• Matthias Gehringer and
• Karl-Heinz Altmann

Beilstein J. Org. Chem. 2017, 13, 1596–1660, doi:10.3762/bjoc.13.159

Strategies toward protecting group-free glycosylation through selective activation of the anomeric center

• A. Michael Downey and
• Michal Hocek

Beilstein J. Org. Chem. 2017, 13, 1239–1279, doi:10.3762/bjoc.13.123

• linchpin for protecting-group-free glycosylation is an exploitation of the differential reactivity of the anomeric center. Two key features of the anomeric center provide this possibility. Firstly, the anomeric position of all unprotected monosaccharides is a reducing end (i.e., in equilibrium as an

Aqueous semisynthesis of C-glycoside glycamines from agarose

• Juliana C. Cunico Dallagnol,
• Alexandre Orsato,
• Diogo R. B. Ducatti,
• Miguel D. Noseda,
• Maria Eugênia R. Duarte and
• Alan G. Gonçalves

Beilstein J. Org. Chem. 2017, 13, 1222–1229, doi:10.3762/bjoc.13.121

• employed for the synthesis of the primary glycamine 3 by means of reductive amination, which could be entirely conducted in aqueous media. Glycamines of monosaccharides have been extensively prepared via reductive amination; however, there are just few and laborious examples for the preparation of 1-deoxy

Sugar-based micro/mesoporous hypercross-linked polymers with in situ embedded silver nanoparticles for catalytic reduction

• Qing Yin,
• Qi Chen,
• Li-Can Lu and
• Bao-Hang Han

Beilstein J. Org. Chem. 2017, 13, 1212–1221, doi:10.3762/bjoc.13.120

• ]. The chemical structure of monosaccharides is commonly a polyhydroxylated aldehyde or ketone with a pyranose ring structure. These hydroxy groups can be easily benzylated to afford sugar-based monomers containing multiple aromatic skeletons. Recently, Liu and Dai have reported a class of novel

• temperature. Results and Discussion All the sugar-based porous organic polymers (SugPOP-1–3) were synthesized by Friedel–Crafts reaction using FDA as an external cross-linker in a similar way. The preparation routes are shown in Scheme 1. Using benzylated monosaccharides as monomers and FDA as the cross

• unaltered during the whole process [18]. Conclusion The preparation of hypercross-linked polymers based on perbenzylated monosugars by Friedel–Crafts reaction using FDA as an external cross-linker is reported. Considering that the features of the polyhydroxylated structures derived from the monosaccharides

Glycoscience@Synchrotron: Synchrotron radiation applied to structural glycoscience

• Serge Pérez and
• Daniele de Sanctis

Beilstein J. Org. Chem. 2017, 13, 1145–1167, doi:10.3762/bjoc.13.114

• three to six anti-parallel β-strands. As a large proportion of crystal structures are complexed with carbohydrates (from monosaccharides to oligosaccharides), three CBM types have been classified based on their sugar recognition modes: surface binders, ”endo-type” binders and “exo-type” binders [44

• ]. Lectins: Lectins constitute a unique and diverse family of proteins that reversibly bind monosaccharides and oligosaccharides, with utmost specificity, without displaying any catalytic or immunological activity. At the present time, the number of crystal structures of lectins deposited in the PDB amounts

• to about 1,500. Interestingly, about 60% of them were obtained ligated to carbohydrates, which range from monosaccharides to 10 residue-long oligosaccharides. Lectins occur in plants, animals, algae, bacteria, fungi and yeasts, and viruses. Their involvement in key biologically-important recognition

Urea–hydrogen peroxide prompted the selective and controlled oxidation of thioglycosides into sulfoxides and sulfones

• Adesh Kumar Singh,
• Varsha Tiwari,
• Kunj Bihari Mishra,
• Surabhi Gupta and
• Jeyakumar Kandasamy

Beilstein J. Org. Chem. 2017, 13, 1139–1144, doi:10.3762/bjoc.13.113

• , oxidation susceptible olefin functional groups were found to be stable during the oxidation of sulfide. Keywords: monosaccharides; oxidation; sulfones; sulfoxides; thioglycosides; urea–hydrogen peroxide; Introduction Organosulfur compounds such as sulfides, sulfoxides and sulfones are useful intermediates

• sulfone in 89% and 91%, respectively. Further, we have studied the oxidation of protected glucosamine thioglycoside (Table 2, entry 15) which provided 91% of sulfoxide and 82% of sulfone. The scope of the oxidation reaction was subsequently investigated with other monosaccharides such as galacto and

Correction: Fluorescent carbon dots from mono- and polysaccharides: synthesis, properties and applications

• Stephen Hill and
• M. Carmen Galan

Beilstein J. Org. Chem. 2017, 13, 1136–1138, doi:10.3762/bjoc.13.112

• Stephen Hill M. Carmen Galan School of Chemistry, University of Bristol, Cantock’s Close, Bristol BS8 1TS, UK 10.3762/bjoc.13.112 Keywords: fluorescent carbon dots; monosaccharides; nanomaterials; nanotechnology applications; polysaccharides; Our original publication showns some errors in the

Fluorescent carbon dots from mono- and polysaccharides: synthesis, properties and applications

• Stephen Hill and
• M. Carmen Galan

Beilstein J. Org. Chem. 2017, 13, 675–693, doi:10.3762/bjoc.13.67

• challenges. Keywords: fluorescent carbon dots; monosaccharides; nanomaterials; nanotechnology applications; polysaccharides; Introduction Nanotechnology applied to biological and biomedical problems has seen an explosion of research in recent years [1]. Functional nanomaterials that can carry biologically

• of novel FCDs with improved properties. For example, simple monosaccharides such as glucose, glucosamine, mannose, fructose and their derivatives and common disaccharides, e.g., sucrose, lactose, and maltose have been employed to prepare fluorescent carbon dots (FCDs) using different methodologies

• their differences allow tailoring of the CD structure and properties [25]. In this review, we focus on the most recent approaches developed to prepare fluorescent CDs using mono-, oligo- and polysaccharides as the main carbon source. Review Fluorescent carbon dots synthesised from monosaccharides

Total synthesis of a Streptococcus pneumoniae serotype 12F CPS repeating unit hexasaccharide

• Peter H. Seeberger,
• Claney L. Pereira and
• Subramanian Govindan

Beilstein J. Org. Chem. 2017, 13, 164–173, doi:10.3762/bjoc.13.19

• steps. Attempted synthesis of hexasaccharide repeating unit 36 via a convergent [3 + 3] glycosylation strategy and exploratory control experiments. A) Failed [3 + 3] glycosylation; B) failed model [1 + 3] glycosylation; C) low yielding model coupling of two monosaccharides. Linear assembly of fully

Interactions between cyclodextrins and cellular components: Towards greener medical applications?

• Loïc Leclercq

Beilstein J. Org. Chem. 2016, 12, 2644–2662, doi:10.3762/bjoc.12.261

• derived from monosaccharides by reduction of the carbonyl group, by oxidation of at least one functional group at the end of the chain in carboxylic acid, by replacement of one or more hydroxy groups by a hydrogen atom, an amine, a thiol or any similar group are also called carbohydrates. Carbohydrates

TMSBr-mediated solvent- and work-up-free synthesis of α-2-deoxyglycosides from glycals

• Mei-Yuan Hsu,
• Yi-Pei Liu,
• Sarah Lam,
• Su-Ching Lin and
• Cheng-Chung Wang

Beilstein J. Org. Chem. 2016, 12, 1758–1764, doi:10.3762/bjoc.12.164

• -glucosides were formed in their corresponding products 33 (71%, 5:1, Table 3, entry 9) and 34 (79%, 4:1, Table 3, entry 10). For the use of monosaccharides as acceptors, primary monosaccharides 22 and 23 gave disaccharides 35 (80%, Table 3, entry 11) and 36 (78%, Table 3, entry 12) respectively in high

• our study, the glycosylation of per-O-acetylated glucal 1 with aliphatic alcohols 12–19 showed better α-selectivities as compared to the per-O-benzylated glucal 3. However, with amino acid derivatives 20 and 21 and monosaccharides 22–24 as acceptors, similar α-selectivities were attained with both

Elucidation of a masked repeating structure of the O-specific polysaccharide of the halotolerant soil bacteria Azospirillum halopraeferens Au4

• Elena N. Sigida,
• Yuliya P. Fedonenko,
• Alexander S. Shashkov,
• Nikolay P. Arbatsky,
• Evelina L. Zdorovenko,
• Svetlana A. Konnova,
• Vladimir V. Ignatov and
• Yuriy A. Knirel

Beilstein J. Org. Chem. 2016, 12, 636–642, doi:10.3762/bjoc.12.62

• ) in the ratios ~1:1.9:2.8:2.2:2.1 (detector response data). In the present work, 2-O-methyl-6-deoxyhexose was identified as L-Rha2Me by GLC, GLC–MS and NMR (see below). Substitution patterns of the monosaccharides in the OPS were determined using alkylation analysis. Earlier, 2,3,4,6-tetra-O

• degradation was used, which included periodate oxidation of the vicinal hydroxy groups in the monosaccharides, mild acidic hydrolysis at the linkages of the destroyed sugar residues, and borohydride reduction of aldehyde groups before and after hydrolysis [17]. Based on the methylation analysis data (see

• spin systems for glycerol (Gro) derived from the 2-substituted Xyl and manno (Rha)- and galacto (Fuc)-configurated monosaccharides (Scheme 1). The spectra of compound 2 also showed signals for a methyl group (δH 3.47–3.48, δC 59.9). The values of 13C NMR chemical shifts of the C-5 signals of Rha 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

• obtained (i.e., 13a) were then used either to acylate monosaccharides (i.e., galactose to give 13b) in order to increase the solubility of the parent compounds in aqueous solutions (Figure 4) or as co-monomers in radical (AIBN)-catalyzed polymerizations (see next paragraph). In recent years linking