Synthesis of multiply fluorinated N-acetyl-D-glucosamine and D-galactosamine analogs via the corresponding deoxyfluorinated glucosazide and galactosazide phenyl thioglycosides

• Vojtěch Hamala,
• Lucie Červenková Šťastná,
• Martin Kurfiřt,
• Petra Cuřínová,
• Martin Dračínský and
• Jindřich Karban

Beilstein J. Org. Chem. 2021, 17, 1086–1095, doi:10.3762/bjoc.17.85

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

• host proteins and cell types, for example the invariant N-acetyl-D-glucosamine or N-acetyl-D-galactosamine residues that attach N- or O-glycans, respectively, to the peptide side chains, the large variety and possible permutations of “capping” residues (for example D-mannopyranosides, D

• membrane is surrounded by a peptidoglycan layer (PG) consisting of multiple, parallel glycan chains of alternating (1→4)-linked subunits of N-acetyl-β-D-glucosamine and N-acetyl- or N-glycolyl-β-D-muramic acid, crosslinked via short conserved oligopeptide stems [44][45]. The PG is covalently attached to

• : filamentous hemagglutinin; L-Fucp: L-fucopyranoside; D-Galf: D-galactofuranoside; D-Galp: D-galactopyranoside; D-GlcNAc: N-acetyl-D-glucosamine; D-Glcp: D-glucopyranoside; HBHA: heparin-binding hemagglutinin; KDO: 3-deoxy-D-manno-octulosonic acid; LAM: lipoarabinomannan; LM: lipomannan; LPS

D-Fructose-based spiro-fused PHOX ligands: synthesis and application in enantioselective allylic alkylation

• Michael R. Imrich,
• Jochen Kraft,
• Cäcilia Maichle-Mössmer and
• Thomas Ziegler

Beilstein J. Org. Chem. 2018, 14, 2082–2089, doi:10.3762/bjoc.14.182

• nucleophile [13][14]. The design of new PHOX ligands is still subject to current research and the synthesis of a lot of different PHOX ligands have been reported during the last years [15][16][17][18]. Kunz reported the preparation of a carbohydrate based PHOX ligand 2 [19]. The starting material was D

• -glucosamine and the sugar was linked to the aromatic system via an annulated oxazoline. Palladium complexes of 2 were used in allylic substitution of allyl acetates with dimethyl malonate as nucleophile and ee values from 69% to 98% were obtained [19]. Recently, we presented the synthesis of carbohydrate

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

• for completion to afford the corresponding azido compound 7 in 82% yield. As anticipated, the anomeric azidation of peracetylated ribofuranose (Table 1, entry 7) proceeded well even at 0 °C within 2 h to give the product in 93% yield. However, the azidation of peracetylated 2-deoxy-D-glucosamine was

• slow and required one equivalent of AuBr3 and heating at 55 °C for 48 h to reach completion. In this case the desired product β-azido 2,3,4,6-acetyl-D-glucosamine (9) could be obtained in 74% yield. The need of using higher amounts of catalyst in this reaction could be attributed to the possible

Diosgenyl 2-amino-2-deoxy-β-D-galactopyranoside: synthesis, derivatives and antimicrobial activity

• Henryk Myszka,
• Patrycja Sokołowska,
• Agnieszka Cieślińska,
• Andrzej Nowacki,
• Maciej Jaśkiewicz,
• Wojciech Kamysz and
• Beata Liberek

Beilstein J. Org. Chem. 2017, 13, 2310–2315, doi:10.3762/bjoc.13.227

• -ethyl derivative of D-glucosamine. Apart from N-ethyl also N-acetyl and 2-chloroethylureido derivatives exhibit activity against Gram-positive bacteria. The change of D-glucosamine into D-galactosamine in diosgenyl 2-amino-2-deoxy-β-D-glycopyranoside impairs the antimicrobial properties of its

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

• components in drug-delivery applications. Chitin, which is a cheap and readily available linear polysaccharide comprised of β-1,4-linked N-acetyl-D-glucosamine units, is the second most abundant biopolymer in nature and forms the backbone of crustaceans and insects exoskeleton and is also found in the cell

• long-term, bench stable fluorescence. These results might suggest further opportunities in the field for these type of less water soluble N-containing polysaccharides. Hyaluronic acid is another N-containing polysaccharide composed of repeating dimeric units of glucoronic acid and N-acetyl-D

• -glucosamine units and which forms the core of complex proteoglycan aggregates found in the extracellular matrix [57]. The team of Du and Shao et al. reported the synthesis of N-doped hyaluronic acid-derived CDs and their application as drug delivery vectors [59]. Following standard hydrothermal synthetic

O-Alkylated heavy atom carbohydrate probes for protein X-ray crystallography: Studies towards the synthesis of methyl 2-O-methyl-L-selenofucopyranoside

• Roman Sommer,
• Dirk Hauck,
• Annabelle Varrot,
• Anne Imberty,
• Markus Künzler and
• Alexander Titz

Beilstein J. Org. Chem. 2016, 12, 2828–2833, doi:10.3762/bjoc.12.282

• activated due to their enhanced reactivity in the presence of other chalcogen-containing glycosides such as O- or S-glycosides. By exploiting these properties, one-pot multi-step glycosylation reactions have been developed recently [10][11]. Natural selenosugars, such as methylseleno N-acetyl-β-D

• -glucosamine, have been described in rats as metabolites for detoxifying inorganic selenite intake [12][13]. Selenium-containing compounds are also widely used as tools for protein X-ray crystallography in structural biology. The determination of a protein structure depends on the correct phase recovering

Mutagenic activity of quaternary ammonium salt derivatives of carbohydrates

• Barbara Dmochowska,
• Karol Sikora,
• Anna Woziwodzka,
• Jacek Piosik and
• Beata Podgórska

Beilstein J. Org. Chem. 2016, 12, 1434–1439, doi:10.3762/bjoc.12.138

• . The polymers (oligosaccharides) of D-glucose found, for example, in wood (cellulose) and D-glucosamine present in shells of crabs and insects (chitin), are the widely known ones [1][2]. Another class of carbohydrate biopolymer derivatives – D-ribose and 2-deoxy-D-ribose – constitutes the backbone of

Synthesis and in vitro cytotoxicity of acetylated 3-fluoro, 4-fluoro and 3,4-difluoro analogs of D-glucosamine and D-galactosamine

• Štěpán Horník,
• Lucie Červenková Šťastná,
• Petra Cuřínová,
• Jan Sýkora,
• Kateřina Káňová,
• Roman Hrstka,
• Ivana Císařová,
• Martin Dračínský and
• Jindřich Karban

Beilstein J. Org. Chem. 2016, 12, 750–759, doi:10.3762/bjoc.12.75

• Background: Derivatives of D-glucosamine and D-galactosamine represent an important family of the cell surface glycan components and their fluorinated analogs found use as metabolic inhibitors of complex glycan biosynthesis, or as probes for the study of protein–carbohydrate interactions. This work is

• focused on the synthesis of acetylated 3-deoxy-3-fluoro, 4-deoxy-4-fluoro and 3,4-dideoxy-3,4-difluoro analogs of D-glucosamine and D-galactosamine via 1,6-anhydrohexopyranose chemistry. Moreover, the cytotoxicity of the target compounds towards selected cancer cells is determined. Results: Introduction

• more than cisplatin and 5-fluorouracil (IC50 28 ± 3 μM and 54 ± 5 μM, respectively). Conclusion: A complete series of acetylated 3-fluoro, 4-fluoro and 3,4-difluoro analogs of D-glucosamine and D-galactosamine is now accessible by 1,6-anhydrohexopyranose chemistry. Intermediate fluorinated 1,6-anhydro

Self and directed assembly: people and molecules

• Tony D. James

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

• electron transfer (PET) cation sensors developed by A. P. De Silva. (b) Fluorescence photoinduced electron transfer (PET) saccharide sensor. (c) Fluorescence AND logic sensors for D-glucosamine hydrochloride. (a) Pyrene diboronic acids (n = 3–8). (b) Pyrene monoboronic acid. (c) Block chart showing 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

• Streptomycetes [5][6][7][8][9][10]. It consists of an N-acetylcysteine, a D-glucosamine, and a D-myo-inositol moiety (Figure 1). D-Glucosamine is α-linked to D-myo-inositol at the 1-position, and N-acetylcysteine is linked to the amino group of D-glucosamine. The conformation of MSH has been investigated by NMR

Synthesis, antimicrobial and cytotoxicity evaluation of new cholesterol congeners

• Mohamed Ramadan El Sayed Aly,
• Hosam Ali Saad and
• Shams Hashim Abdel-Hafez

Beilstein J. Org. Chem. 2015, 11, 1922–1932, doi:10.3762/bjoc.11.208

• singlet at δ = 7.78 ppm confirming the cycloaddition of derivatives 3 and 10. D-Glucosamine is an essential constituent of many naturally occurring oligosaccharides such as bacterial and fungal cell walls. Mainly, it is available as N-acetylglucosamine in β-glycosidic linkages (β-D-GlcNAc) [37

Synthesis and evaluation of the biostability and cell compatibility of novel conjugates of nucleobase, peptidic epitope, and saccharide

• Dan Yuan,
• Xuewen Du,
• Junfeng Shi,
• Ning Zhou,
• Abdulgader Ahmed Baoum,
• Khalid Omar Al Footy,
• Khadija Omar Badahdah and
• Bing Xu

Beilstein J. Org. Chem. 2015, 11, 1352–1359, doi:10.3762/bjoc.11.145

• chain from the resin with 95% trifluoroacetic acid (TFA) without N-protecting groups. Later, NAS was obtained by reacting D-glucosamine hydrochloride with the fully protected NA. After cleaving the protecting group on amino acids with 95% TFA, we used reversed-phase high-performance liquid

• solid-phase peptide synthesis and liquid-phase synthesis). i) Fmoc-Val-OH, DIPEA; ii) 20% piperidine; iii) Fmoc-Pro-OH, HBTU, DIPEA; iv) Fmoc-Thr(t-Bu)-OH, HBTU, DIPEA; v) thymine-1-acetic acid, HBTU, DIPEA; vi) TFE/DCM 2:8; vii) D-glucosamine hydrochloride, HBTU, DIPEA; viii) TFA/H2O 95:5

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

• . Keywords: antimicrobial activities; D-glucosamine; diosgenin glycosylation; N-alkylation; Introduction Saponins are a group of steroid or triterpenoid glycosides, widely distributed in the plant kingdom [1]. Saponins are characteristic by their foaming properties in aqueous solution, causing them to be

• -hydroxy derivatives of D-glucose and L-rhamnose [49]. Glycosylation of diosgenin with twelve different derivatives of D-glucosamine (2a–d, 3a–d, and 5a–d), was examined using “normal” and “reverse” procedures [50] (Table 1). In the “normal” procedure, the promoter (silver triflate or trimethylsilyl

Synthesis and characterization of pH responsive D-glucosamine based molecular gelators

• Navneet Goyal,
• Hari P. R. Mangunuru,
• Bargav Parikh,
• Sonu Shrestha and
• Guijun Wang

Beilstein J. Org. Chem. 2014, 10, 3111–3121, doi:10.3762/bjoc.10.328

• for soft biomaterials. Low molecular weight hydrogelators are especially useful for exploring biomedical applications. Previously, we found that 4,6-O-benzylidene acetal protected D-glucose and D-glucosamine are well-suited as building blocks for the construction of low molecular weight gelators. To

• better understand the scope of D-glucosamine derivatives as gelators, we synthesized and screened a novel class of N-acetylglucosamine derivatives with a p-methoxybenzylidene acetal protective group. This modification did not exert a negative influence on the gelation. On the contrary, it actually

• 16 under the same acidic conditions are shown in Figure S3 (Supporting Information File 1), and the full range of UV spectra of the released naproxen are shown in Figure S4, Supporting Information File 1. Conclusion In summary, we have synthesized and studied a new series of D-glucosamine derivatives

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

• and chitosan derivatives for pharmaceutical applications was described [22]. Chitosan is the polysaccharide obtained from the abundant chitin by alkali or enzymatic degradation. It consists of a backbone of β-(1→4)-linked D-glucosamine units with a variable degree of N-acetylation. The protonated

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

• well-known role in interactions between plants and bacteria [16][17][18][19][20][21]. Recently, Sigida et al. reported the structure of the repeating unit of the LPS present in the cell wall of Azospirillum brasilense strain Sp7: a tetrasaccharide consisting of D-galactose, D-glucosamine, L-rhamnose

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

• containing D-glucosamine, L-rhamnose, D-glucose and D-galactofuranose moieties in a 1:1:1:1 ratio (Figure 1). The emergence of multi drug resistant bacterial strains forces medicinal chemists to develop new approaches to combat bacterial infections. Since the structure of the O-antigen influences the

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

• azide during the scale-up of the reaction but this caused a decrease of the overall reaction yields. In all cases, the test reactions were performed starting from D-glucosamine hydrochloride as a model compound for the synthesis of 1,3,4,6-tetra-O-acetyl-N-azidoacetyl-D-glucosamine (Ac4GlcNAz = 1

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

• with alpha and beta linkage, one beta-linked D-glucosamine and one beta-linked D-mannosyl moiety (Figure 1). Although several therapeutics have appeared in the past to control the diarrheal epidemics caused by E. coli infections, emergence of resistant strains is a serious concern in the development of

The Amadori rearrangement as glycoconjugation method: Synthesis of non-natural C-glycosyl type glycoconjugates

• Katharina Gallas,
• Gerit Pototschnig,
• Florian Adanitsch,
• Arnold E. Stütz and
• Tanja M. Wrodnigg

Beilstein J. Org. Chem. 2012, 8, 1619–1629, doi:10.3762/bjoc.8.185

• mixture of the unreacted lactone 4, the fully reduced alditol 6 as the main product, and a small amount of the desired aldoheptose 5 was formed. When N-acetyl-D-glucosamine was subjected to this reduction method, the corresponding heptitol 6 was isolated as the main product under all conditions tried

Kinetic studies and predictions on the hydrolysis and aminolysis of esters of 2-S-phosphorylacetates

• Milena Trmčić and
• David R. W. Hodgson

Beilstein J. Org. Chem. 2010, 6, 732–741, doi:10.3762/bjoc.6.87

• a thiophosphate nucleophile from commonly used bromoacetate ester cross-linking agents. Results: We found cross-linking between uridine-5′-monophosphorothioate and D-glucosamine using N-hydroxybenzotriazole and N-hydroxysuccinimde bromoacetates to be ineffective. In order to gain insight into these

• preliminary studies into thiophosphate-amine cross-linking using both N-hydroxybenzotriazole 1 (R = Bt) and N-hydroxysuccinimde 1 (R = NHS) esters of bromoacetic acid with thiophosphate 4 and D-glucosamine as a representative thiophosphate and a representative amine, respectively (Scheme 2). A mixed water

• of pHs. D-Glucosamine was chosen as a model amine system to investigate these properties because of its relatively low pKaH of 7.75 [7]. Thus, even at relatively low pHs, a substantial proportion of the amine will be in its neutral, nucleophilic form. In addition, by structural analogy with

Molecular recognition of organic ammonium ions in solution using synthetic receptors

• Andreas Späth and
• Burkhard König

Beilstein J. Org. Chem. 2010, 6, No. 32, doi:10.3762/bjoc.6.32

Bis(oxazolines) based on glycopyranosides – steric, configurational and conformational influences on stereoselectivity

• Tobias Minuth and
• Mike M. K. Boysen

Beilstein J. Org. Chem. 2010, 6, No. 23, doi:10.3762/bjoc.6.23

• Tobias Minuth Mike M. K. Boysen Institute of Organic Chemistry, Gottfried-Wilhelm-Leibniz University of Hannover, Schneiderberg 1B, D-30167 Hannover, Germany 10.3762/bjoc.6.23 Abstract In previous studies we found that the asymmetric induction of bis(oxazolines) based on D-glucosamine strongly

• though N-acylated derivatives of D-glucosamine easily form bicyclic carbohydrate oxazolines, until recently only a few examples of mono(oxazoline) ligands [15][16][17] and the corresponding bis(oxazolines) [18] based on this monosaccharide have appeared in the literature. In the course of our work we

• new ligands in stereoselective cyclopropanation. Results and Discussion The synthesis of all new ligands started from the known thioglucoside 7 [24] which was also employed as key intermediate for the preparation of ligands 3a–f [20][21] and is accessible from D-glucosamine in 5 steps and 57% overall

Mitomycins syntheses: a recent update

• Jean-Christophe Andrez

Beilstein J. Org. Chem. 2009, 5, No. 33, doi:10.3762/bjoc.5.33

• ), D-glucosamine 21 and carbamoyl phosphate (Scheme 4) [29][30][31][32]. The key intermediate, AHBA, is also a common precursor to other anticancer drugs, such as rifamycin and ansamycin. 2.2. Mode of action Mitomycins are quinone antitumor antibiotics that exert their biological activity through DNA