N-Glycosides of indigo, indirubin, and isoindigo: blue, red, and yellow sugars and their cancerostatic activity

• Peter Langer

Beilstein J. Org. Chem. 2024, 20, 2840–2869, doi:10.3762/bjoc.20.240

• isatin-N-glycosides derived from β-ᴅ-galactose, β-ᴅ-glucose, and β-ᴅ-xylose which might be due to their 1,2-trans configuration. An identical relative configuration (1,2-trans; 1,3-cis) is observed for the first three carbon atoms of β-ᴅ-galactose, β-ᴅ-glucose, and β-ᴅ-xylose. In contrast, for β-ᴅ

Introduction of a human- and keyboard-friendly N-glycan nomenclature

• Friedrich Altmann,
• Johannes Helm,
• Martin Pabst and
• Johannes Stadlmann

Beilstein J. Org. Chem. 2024, 20, 607–620, doi:10.3762/bjoc.20.53

• always the same core. Years later, colleagues from in- and outside my institution engaged in “humanization” of plant N-glycans, which at first entailed removal of the plant-typical residues α1,3-fucose and xylose [32][33]. Later, the glyco-engineering of plants with the introduction of human features

• triantennary N-glycans only, we will deal with it in the relevant chapter below. Core-fucosylation, bisecting GlcNAc and xylose The core fucose constitutes a third terminal residue and hence we introduce a third structure term, “F” for fucose. We could simply write, e.g., A4A4F. In mammals, the core fucose is

• plants and some non-vertebrate animals [43][44], the β-mannosyl residues may instead be decorated with a xylose residue, for which the letter X is added after the term for the 3-arm (Figure 4). Fucose on antennae Lewis fucoses introduce branching of the antenna. IUPAC nomenclature uses square brackets to

A myo-inositol dehydrogenase involved in aminocyclitol biosynthesis of hygromycin A

• Michael O. Akintubosun and
• Melanie A. Higgins

Beilstein J. Org. Chem. 2024, 20, 589–596, doi:10.3762/bjoc.20.51

• scyllo-inositol but can have reduced activity on ᴅ-chiro-inositol, ᴅ-glucose, ᴅ-xylose and 4-O-benzyl-myo-inositol [12][13][15][16][17]. However, scyllo-inositol dehydrogenases are active on scyllo-inositol and myo-inositol to a lesser extent [16][18]. Altogether, this suggests that Hyg17 can accommodate

Synthesis of sulfur karrikin bioisosteres as potential neuroprotectives

• Martin Pošta,
• Václav Zima,
• Lenka Poštová Slavětínská,
• Marika Matoušová and
• Petr Beier

Beilstein J. Org. Chem. 2022, 18, 549–554, doi:10.3762/bjoc.18.57

• (14), respectively, following a published procedure [21][23], while karrikin KAR2 (2) was synthesized from ᴅ-xylose [24]. The conversion of karrikins 1–4 to the corresponding C2 thiones 9–12 was accomplished using microwave-assisted heating with Lawesson’s reagent and hexamethyldisiloxane (HMDO

• Goddard-Borger [24] for the preparation of 2 using the Xavier’s procedure [33] towards 5-thiopyranose-fused butenolides and the reaction pathway is outlined in Scheme 5. The synthesis of the key intermediate butenolide 23 was accomplished starting from easily available ᴅ-xylose, following a published

Glycosylated coumarins, flavonoids, lignans and phenylpropanoids from Wikstroemia nutans and their biological activities

• Meifang Wu,
• Xiangdong Su,
• Yichuang Wu,
• Yuanjing Luo,
• Ying Guo and
• Yongbo Xue

Beilstein J. Org. Chem. 2022, 18, 200–207, doi:10.3762/bjoc.18.23

• . The ROESY spectrum (Supporting Information File 1, Figure S34, recorded in DMSO-d6) showed correlations of H-3'' and H-1'' /H-5''/HO-4'', indicating the ᴅ-configuration of glucose, while the ROESY correlations of H-1'''/H-3'''/H-5''', H-3'''/H-5''', and H-2'''/H-4''' implied the xylose should be in ᴅ

• by a ROESY correlation between H-6'' and H-1'''. Subsequently, an acid hydrolysis of 1 afforded the products including daphnogitin, a ᴅ-glucose, and a ᴅ-xylose. The absolute configurations of glucopyranosyl and xylopyranosyl was further determined by HPLC analysis of the sugar derivatives (Supporting

• and sugar, respectively. The aqueous residue was concentrated to dryness under N2. The aqueous residue, ᴅ-glucose (2 mg), and ᴅ-xylose standard (2 mg) were separately dissolved in 0.5 mL anhydrous pyridine, and ʟ-cysteine methyl ester hydrochloride (2.0 mg) was then added. Each reaction mixture was

Progress and challenges in the synthesis of sequence controlled polysaccharides

• Giulio Fittolani,
• Theodore Tyrikos-Ergas,
• Denisa Vargová,
• Manishkumar A. Chaube and
• Martina Delbianco

Beilstein J. Org. Chem. 2021, 17, 1981–2025, doi:10.3762/bjoc.17.129

• recognition by plant cell-wall antibodies. To avoid performing the challenging 1,2-cis glycosylation that would generate a mixture of anomers in AGA, the α(1–6) linkage between glucose and xylose was pre-installed in the disaccharide BB 16 (Scheme 3, highlighted in red) [104]. The orthogonal levulinoyl (Lev

• strategy in AGA has already shown promising results [182] and could fuel the production of well-defined polysaccharides based on multiple 1,2-cis-glycosidic linkages. Xylose-based polysaccharides Xylans are abundant polysaccharides mainly found in plants or in mammalian cells as proteoglycans [189][190

A systems-based framework to computationally describe putative transcription factors and signaling pathways regulating glycan biosynthesis

• Theodore Groth,
• Rudiyanto Gunawan and
• Sriram Neelamegham

Beilstein J. Org. Chem. 2021, 17, 1712–1724, doi:10.3762/bjoc.17.119

• common core carbohydrate sequence attaching them to the corresponding proteins. These are constructed by the activity of specific xylotransferases (XYLT1 and XYLT2), galactosyltransferses B4GALT7 and B3GALT6 that sequentially add two galactose residues to xylose, and the glucuronyltransferase B3GAT3 that

• adds glucuronic acid to the terminal galactose. Also involved in the formation of this core is FAM20B, a kinase that 2-O-phosphorylates xylose. At this point, the addition of GalNAc to GlcA by CSGALNACT1 and 2 results in the initiation of chondroitin sulfate chains. The attachment of GlcNAc by EXTL3 to

A comprehensive review of flow chemistry techniques tailored to the flavours and fragrances industries

• Guido Gambacorta,
• James S. Sharley and
• Ian R. Baxendale

Beilstein J. Org. Chem. 2021, 17, 1181–1312, doi:10.3762/bjoc.17.90

How and why plants and human N-glycans are different: Insight from molecular dynamics into the “glycoblocks” architecture of complex carbohydrates

• Carl A. Fogarty,
• Aoife M. Harbison,
• Amy R. Dugdale and
• Elisa Fadda

Beilstein J. Org. Chem. 2020, 16, 2046–2056, doi:10.3762/bjoc.16.171

• relationships in complex carbohydrates, with important implications in glycoengineering design. Keywords: complex carbohydrates; fucose; glycoblocks; molecular dynamics; molecular recognition; N-glycans; xylose; Introduction Complex carbohydrates (or glycans) are an essential class of biomolecules, directly

• ][21][22][23]. More specifically, we investigate how core α(1-3)-linked fucose (Fuc) and β(1-2)-linked xylose (Xyl) affect the structure and dynamics of plants N-glycoforms [23] and of hybrid constructs with mammalian N-glycoforms [24]. At first glance plants protein N-glycosylation [23] is quite

• the reader. As shown in Tables S1 and S2 in Supporting Information File 1, the equilibrium of the (1-3) arm is not affected by core α(1-3)-Fuc. β(1-2) xylose in plant N-glycans: Because the β(1-2)-Xyl sits in front of the two arms, it greatly affects their dynamics. Because of steric hindrance, the (1

Recent synthesis of thietanes

• Jiaxi Xu

Beilstein J. Org. Chem. 2020, 16, 1357–1410, doi:10.3762/bjoc.16.116

• approach, the thietane ring was constructed more efficiently through a two-step displacement sequence from the D-xylose-derived dimesylate 114 (Scheme 24). The first step displacement involved the selective SN2 reaction of the primary mesylate with KSAc to yield a monothioacetate 115 in 80% yield. The

• series of thietanose nucleosides 118 [53]. Similarly, enatiomeric thietanose nucleosides 123 were prepared from L-xylose [53] (Scheme 24). In 2010, Takahata and co-workers designed and synthesized thietane-fused nucleosides. They first prepared a key intermediate spiro acetal 125, which was converted

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

An overview on recent advances in the synthesis of sulfonated organic materials, sulfonated silica materials, and sulfonated carbon materials and their catalytic applications in chemical processes

• Hashem Sharghi,
• Pezhman Shiri and
• Mahdi Aberi

Beilstein J. Org. Chem. 2018, 14, 2745–2770, doi:10.3762/bjoc.14.253

• triglycerides with methanol, the etherification of isopentene with methanol, the esterification of palm fatty acid distillate with methanol, the dehydration of D-xylose into furfural, the production of ethyl acetate from ethanol and acetic acid, and the transesterification of palm oil with methanol into biodiesel

• esterification under atmospheric conditions and conventional heating [75]. The catalyst showed excellent catalytic activity in the dehydration of D-xylose (139) into furfural (140) as an industrial platform molecule as well as the production of ethylacetate from ethanol and acetic acid [76]. The dehydration of D

• -xylose (139) into furfural (140) was performed in water-CPME (1:3, v/v) and heated in a commercial monowave microwave oven in the presence of 10 wt % of 138 for 50 min. A maximum furfural yield of 76% was obtained. A new sulfonated graphene catalyst GR-SO3H (145) was prepared in some steps. A mixture of

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

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

An eco-compatible strategy for the diversity-oriented synthesis of macrocycles exploiting carbohydrate-derived building blocks

• Sushil K. Maurya and
• Rohit Rana

Beilstein J. Org. Chem. 2017, 13, 1106–1118, doi:10.3762/bjoc.13.110

• sequence of protection-deprotection-functionalization reactions at appropriate position (Figure 1). D-glucose, D-xylose and L-arabinose were used as the key starting materials for the DOS protocol. It was expected that each given sugar building block (generated in the building phase of the DOS) could be

• as metathesis substrates for the synthesis of novel sugar embedded macrocyclic molecules. Cycloaddition of xylose derived azide building blocks containing a primary azido group (2a) produced similar yields (i.e., 3a, 3b and 3d) with xylose and arabinose derived building blocks containing a propargyl

• ether group on the primary OH group (1a and 1c) or xylose derived building block containing a propargyl group on the secondary OH group (1b). Further, a comparatively lower yield for the cycloaddition reaction (3c) was obtained when both building blocks used contain a secondary azide group (2b) and a

First total synthesis of kipukasin A

• Chuang Li,
• Haixin Ding,
• Zhizhong Ruan,
• Yirong Zhou and
• Qiang Xiao

Beilstein J. Org. Chem. 2017, 13, 855–862, doi:10.3762/bjoc.13.86

• -6-methylbenzoyl chloride (9) was used directly in the next step without further purification. Then we started to synthesize glycosylation donor 16 as the key building block (Scheme 2). In previous reports, 3,5-O-diacetyl-1,2-O-isopropylidene-D-ribofuranose (11) was prepared either from D-xylose [29

Revaluation of biomass-derived furfuryl alcohol derivatives for the synthesis of carbocyclic nucleoside phosphonate analogues

• Bemba Sidi Mohamed,
• Christian Périgaud and
• Christophe Mathé

Beilstein J. Org. Chem. 2017, 13, 251–256, doi:10.3762/bjoc.13.28

• catalytic hydrogenation of furfural; the latter is obtained from the dehydration of xylose, a 5-carbon sugar derived from vegetal biomass. Furfuryl alcohol finds widespread application in the chemical industries and for example is employed for the production of synthetic fibers, fine chemicals, etc. In fine

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

• ] or plant natural products [41]. In order to optimize the synthesis of 3 by avoiding the formation of the furanose acetate 10 and increasing the α-selectivity, we revised our synthetic approach. The problematic formation of furanosides has been reported by Kovac et al. for xylose derivatives bearing a

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

• measurements, the binding constants can be estimated. The obtained results reveal that D-ribose, D- and L-arabinose, D-xylose, D-lyxose, D-2-deoxyribose, and methyl β-D-ribopyranoside were complexed by β-CD (binding constants ≤14 M−1). In contrast, aldohexoses and their derivatives (D-glucose, D-galactose, D

• ] and the binding constants obtained by these three groups are reported in Table 4. These values are relatively close to each other and the sugar/β-CD binding constants increase in the order of D-galactose ≈ D-glucose < D-mannose < D-arabinose < D-xylose < D-ribose. This magnitude is consistent with the

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

• carbohydrate and glycolipid parts [15] followed by fractionation of the released water-soluble carbohydrate portion by Sephadex G-50 Superfine size-exclusion chromatography. It was demonstrated that the OPS contained 2-O-methyl-6-deoxyhexose, L-rhamnose (Rha), D-fucose (Fuc), D-xylose (Xyl), and D-glucose (Glc

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

• -(4-methylbenzoyl)-α-D-xylofuranose (24) was synthesized from D-xylose according to literature procedures [41]. Compound 24 was treated with iodine in methanol, and fluorinated with diethylaminosulfur trifluoride (DAST). The universal intermediate 1’,2’-di-O-acetyl-5’-O-p-toluyl-3’-fluoro-3’-deoxy-β-D

The chemoenzymatic synthesis of clofarabine and related 2′-deoxyfluoroarabinosyl nucleosides: the electronic and stereochemical factors determining substrate recognition by E. coli nucleoside phosphorylases

• Ilja V. Fateev,
• Konstantin V. Antonov,
• Irina D. Konstantinova,
• Tatyana I. Muravyova,
• Frank Seela,
• Roman S. Esipov,
• Anatoly I. Miroshnikov and
• Igor A. Mikhailopulo

Beilstein J. Org. Chem. 2014, 10, 1657–1669, doi:10.3762/bjoc.10.173

• phosphate 12a: ribokinase (2-deoxy-2-fluoro-D-arabinofuranose-5-phosphate), phosphopentomutase (PPN; no 1,6-diphosphates of D-hexoses as co-factors required) (12a), and finally PNP. The substrate activities of D-arabinose, D-ribose and D-xylose in the similar cascade syntheses of the relevant 2

• –8) of 2-chloroadenine starting from 2-deoxy-2-fluoro-D-arabinose, D-arabinose, D-ribose and D-xylose was studied (Figure 1). Results and Discussion α-D-Pentofuranose-1-phosphates 12a and 13a as substrates of the E. coli nucleoside phosphorylases. Recently, we have studied the synthesis of purine and

• -xylofuranosyl)-2-chloroadenine (7) from D-xylose and 2-chloroadenine slowly took place leading to a yield of ca. 8% after 48 h. The cascade one-pot synthesis of clofarabine was investigated in more detail and, like D-arabinose, satisfactory substrate properties of 2-deoxy-2-fluoro-α-D-arabinose and its 5

The search for new amphiphiles: synthesis of a modular, high-throughput library

• George C. Feast,
• Thomas Lepitre,
• Xavier Mulet,
• Charlotte E. Conn,
• Oliver E. Hutt,
• G. Paul Savage and
• Calum J. Drummond

Beilstein J. Org. Chem. 2014, 10, 1578–1588, doi:10.3762/bjoc.10.163

• organic amphiphilic compounds was synthesised consisting of glucose, galactose, lactose, xylose and mannose head groups and double and triple-chain hydrophobic tails. A modular, high-throughput approach was developed, whereby head and tail components were conjugated using the copper-catalysed azide–alkyne

• would provide a wealth of data on the appropriate characteristics for a self-assembled sugar-based amphiphilic drug. Five sugars were chosen for this library: glucose, galactose, lactose, xylose and mannose. Glucose and galactose amphiphiles have been demonstrated to possess slightly different lyotropic

• phase behaviour, despite the relatively small structural difference (epimers) between the two monosaccharides. Xylose does not bear the 6-position side-chain alcohol so it takes up a significantly smaller volume. Lactose is a disaccharide so it has a much larger head-group volume. The four azido-sugars

Molecular architecture with carbohydrate functionalized β-peptides adopting 3₁₄-helical conformation

• Nitin J. Pawar,
• Navdeep S. Sidhu,
• George M. Sheldrick,
• Dilip D. Dhavale and
• Ulf Diederichsen

Beilstein J. Org. Chem. 2014, 10, 948–955, doi:10.3762/bjoc.10.93

• oligomers varying the sugar (glucose, galactose, xylose) and sugar protecting groups. The influence of sugar units and the configuration of sugar-β-amino acids on β-peptide secondary structure were investigated by CD spectroscopy. Keywords: carbohydrate recognition; conformation; glycopeptide; β-peptide

• , xylose) as sugar-β-amino acids in a 314-helix. Up to three sugar units were linearly aligned with 5 Å distance (Figure 1). This kind of sugar organization will be of later relevance, e.g., in lectin binding studies and with respect to the investigation of multivalency effects [21][22][23]. The use of

• peptide solubility in aqueous solution. Therefore, the β-peptide design provides incorporation of D-glucose, D-galactose and D-xylose derived sugar-β-amino acids at every third position (i and i+3). The remaining positions were filled with β-homolysine and ACHC. For ease of synthesis, β-homoglycine amide

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

• -allose production. D-Allose can also be synthesized from inexpensive D-glucose as a starting material via a three-step bioconversion, sequentially catalyzed by D-xylose isomerase (EC 5.3.1.5), D-psicose 3-epimerase, and ribose-5-phosphate isomerase (Scheme 12). The overall conversion yield for the

• ideal starting material for glycoconjugate vaccines against the enteropathogenic bacterium Shigella sonne [80]. Enzymatically, L-glucose can be synthesized by isomerizing L-fructose (Scheme 13) catalyzed by D-xylose isomerase from Candida utilis [81] or whole cells of a mutant Klebsiella pneumoniae