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

• potential of the new eco-compatible approach for the macrocyclic library generation. Keywords: carbohydrate; click chemistry; diversity-oriented synthesis; macrocycles; ring-closing metathesis; Introduction Macrocycles offer very complex molecular architectures with a diverse range of ring sizes decorated

• with many functional groups found application in pharmaceuticals, agrochemicals, cosmetics and materials science [1][2][3][4]. Carbohydrate-embedded macrocycles represent an important class of macrocyclic compounds in which at least two bonds from a monosaccharide residue form a part of the macrocyclic

• easily available commercial products and are well-endowed with functionalities which enable them to establish catalytic sites as well as secondary binding sites [56]. The abundance of various functional groups in the carbohydrate precursor allows for easy access to multiple building blocks by

Glyco-gold nanoparticles: synthesis and applications

• Federica Compostella,
• Olimpia Pitirollo,
• Alessandro Silvestri and
• Laura Polito

Beilstein J. Org. Chem. 2017, 13, 1008–1021, doi:10.3762/bjoc.13.100

• biological events [1]. Nevertheless, carbohydrates interact with their ligands in a very weak manner, so much faint that nature found in the multi-presentation (the so called “glycocalix”) a solution to have efficient carbohydrate interactions. In fact, the sum of binding affinities for single and isolated

• interaction is ever lower than those measured when a glyco-multivalent presentation is exploited [2]. Following nature’s design, carbohydrate multivalent systems are, at the present time, the most common strategy used to study weak carbohydrate–carbohydrate or carbohydrate–protein interactions and the

• , gold can be easily and covalently decorated on its surface by exploiting the strong soft–soft interaction between a Au atom and sulfur [8]. Therefore, glyco-gold nanoparticles (GAuNPs) represent a smart, multimodal and versatile nanoplatform to develop carbohydrate-based nanotechnology and nanomedicine

Total synthesis of TMG-chitotriomycin based on an automated electrochemical assembly of a disaccharide building block

• Yuta Isoda,
• Norihiko Sasaki,
• Kei Kitamura,
• Shuji Takahashi,
• Sujit Manmode,
• Naoko Takeda-Okuda,
• Jun-ichi Tamura,
• Toshiki Nokami and
• Toshiyuki Itoh

Beilstein J. Org. Chem. 2017, 13, 919–924, doi:10.3762/bjoc.13.93

• -chitotriomycin using an automated electrochemical synthesizer for the assembly of carbohydrate building blocks is demonstrated. We have successfully prepared a precursor of TMG-chitotriomycin, which is a structurally-pure tetrasaccharide with typical protecting groups, through the methodology of automated

• synthesizer for the automated electrochemical assembly of carbohydrate building blocks [25]. During the course of our study, we have achieved the synthesis of a potential precursor of TMG-chitotriomycin (1); however, we obtained the tetrasaccharide as a mixture of α- and β-isomers in the terminal glycosidic

• reactions were performed under an Ar atmosphere unless otherwise noted. Materials All materials including solvents were purchased and used without further purification. Carbohydrate building blocks 2a, 2b, and 4 were prepared according to an previous report [11]. Automated synthesis of TMG-chitotriomycin

Expression, purification and structural analysis of functional GABA transporter 1 using the baculovirus expression system

• Jing Hu,
• Chris Weise,
• Christoph Böttcher,
• Hua Fan and
• Jian Yin

Beilstein J. Org. Chem. 2017, 13, 874–882, doi:10.3762/bjoc.13.88

• Jing Hu Chris Weise Christoph Bottcher Hua Fan Jian Yin Wuxi School of Medicine, Key Laboratory of Carbohydrate Chemistry and Biotechnology, Ministry of Education, Jiangnan University, Lihu Avenue 1800, 214122, Wuxi, China Institut für Biochemie und Molekularbiologie, Campus Benjamin Franklin

• 63, Berlin D-14195, Germany Institut für Laboratoriumsmedizin, Klinische Chemie und Pathobiochemie, Charité Universitätsmedizin Berlin, Berlin D-13353, Germany Key Laboratory of Carbohydrate Chemistry and Biotechnology, Ministry of Education, School of Biotechnology, Jiangnan University, Lihu

Opportunities and challenges for the sustainable production of structurally complex diterpenoids in recombinant microbial systems

• Katarina Kemper,
• Max Hirte,
• Markus Reinbold,
• Monika Fuchs and
• Thomas Brück

Beilstein J. Org. Chem. 2017, 13, 845–854, doi:10.3762/bjoc.13.85

• bacterial host is often not trivial due to complex metabolic coherences. The essential steps in establishing successful production of diterpenoid carbohydrate backbones in heterologous systems can be partitioned into three following areas: 1: formation of central isoprenoid precursors, 2: combination of C5

Synthesis of D-manno-heptulose via a cascade aldol/hemiketalization reaction

• Yan Chen,
• Xiaoman Wang,
• Junchang Wang and
• You Yang

Beilstein J. Org. Chem. 2017, 13, 795–799, doi:10.3762/bjoc.13.79

• evaluation of carbohydrate–lectin interactions by conjugation with fluorescent quantum dots via click chemistry [13][14]. Besides, differentially protected D-manno-heptulose building blocks could serve as valuable precursors for the synthesis of C-glycosides [15][16]. The known synthesis of D-manno-heptulose

• protected ketoheptose building block is still attractive due to the versatile functionalization possibilities of the building block into various derivatives of D-manno-heptulose. A de novo synthesis has proved to be an attractive strategy to produce orthogonally protected carbohydrate building blocks from

Cyclodextrins tethered with oligolactides – green synthesis and structural assessment

• Cristian Peptu,
• Mihaela Balan-Porcarasu,
• Alena Šišková,
• Ľudovít Škultéty and
• Jaroslav Mosnáček

Beilstein J. Org. Chem. 2017, 13, 779–792, doi:10.3762/bjoc.13.77

• The properties of cyclodextrin-oligoester covalent conjugates, situated at the border of low and high molecular weight compounds can be influenced by both the carbohydrate and the oligoester components. The properties of such materials like solubility, miscibility with other materials, inclusion

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

• which to synthesise FCDs with distinct features and interesting applications. This mini-review article will cover the progress in the development of FCDs prepared from carbohydrate sources with an emphasis on their synthesis, functionalization and technical applications, including discussions on current

• [13][24]. Similarly, important carbohydrate-based biopolymers such as cellulose, chitin, chitosan, dextran, cyclodextrin, and hyaluronic acid, which differ not only in elemental composition, but also in chemo-physical properties, have also been successfully utilised in the preparation of CDs, where

• our knowledge, the first reported example involving a carbohydrate moiety (Scheme 1) [18]. The water-soluble nanoparticles exhibited an amorphous core, as deduced by X-ray diffraction (XRD), while Fourier-transformed infrared (FTIR) spectroscopy analysis indicated the presence of a range of oxygen

Exploring endoperoxides as a new entry for the synthesis of branched azasugars

• Svenja Domeyer,
• Mark Bjerregaard,
• Henrik Johansson and
• Daniel Sejer Pedersen

Beilstein J. Org. Chem. 2017, 13, 644–647, doi:10.3762/bjoc.13.63

• these building blocks provided access to a variety of derivatives including tetrahydrofurans, epoxides and protected amino-tetraols. Keywords: azasugar; carbohydrate; cycloaddition; endoperoxide; photochemistry; Introduction Azasugars are small organic compounds that can mimic carbohydrates or their

• in treatment of type I Gaucher’s disease and Niemann Pick type C disease (Scheme 1). Historically, azasugars were most commonly synthesised from available carbohydrate starting materials, a strategy that is still extensively employed today [4][5]. However, a variety of alternative synthetic

Biosynthetic origin of butyrolactol A, an antifungal polyketide produced by a marine-derived Streptomyces

• Enjuro Harunari,
• Hisayuki Komaki and
• Yasuhiro Igarashi

Beilstein J. Org. Chem. 2017, 13, 441–450, doi:10.3762/bjoc.13.47

• /carbohydrate/nucleic acid derivatives [1][2]. One of the largest groups of bacterial secondary metabolites is polyketide from which a range of clinically used drugs have been developed. Polyketides still remain in the focus of drug development because of their structural complexity that can provide attractive

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

• ] strategy that was not successful due to steric constraints. The synthetic hexasaccharide is the starting point for further immunological investigations. Keywords: carbohydrate antigen; glycosylation; oligosaccharides; Streptococcus pneumoniae; total synthesis; Introduction Streptococcus pneumoniae is a

• polysaccharides (CPS) that surround them, are responsible for about 90% of infections worldwide [7]. The licensed polysaccharide vaccine Pneumovax 23 contains serotype 12F but is not efficacious in young children or elderly people, those at highest risk. The carbohydrate conjugate vaccines Prevanar13™ and

Silyl-protective groups influencing the reactivity and selectivity in glycosylations

• Mikael Bols and
• Christian Marcus Pedersen

Beilstein J. Org. Chem. 2017, 13, 93–105, doi:10.3762/bjoc.13.12

• silylene protective groups are also becoming increasingly popular. In carbohydrate chemistry silyl protective groups have frequently been used primarily as an orthogonal protective group to the more commonly used acyl and benzyl protective groups. However, silyl protective groups have significantly

• or high stereoselectivity. This mini review will summarize these findings. Keywords: Carbohydrate; conformation; glycosylation; reactivity; selectivity; Introduction Silicon-based protective groups of alcohols have a long history in organic chemistry [1][2][3]. The most popular and commercially

• available silyl-protective groups are trimethylsilyl (TMS), triethylsilyl (TES), tert-butyldimethylsilyl (TBS), tert-butyldiphenylsilyl (TBDPS), triisopropylsilyl (TIPS) as well as the diol-protective groups DTBS and TIPDS (Figure 1). Silyl groups have also early been used in the carbohydrate field to

Iodination of carbohydrate-derived 1,2-oxazines to enantiopure 5-iodo-3,6-dihydro-2H-1,2-oxazines and subsequent palladium-catalyzed cross-coupling reactions

• Michal Medvecký,
• Igor Linder,
• Luise Schefzig,
• Hans-Ulrich Reissig and
• Reinhold Zimmer

Beilstein J. Org. Chem. 2016, 12, 2898–2905, doi:10.3762/bjoc.12.289

• Michal Medvecky Igor Linder Luise Schefzig Hans-Ulrich Reissig Reinhold Zimmer Freie Universität Berlin, Institut für Chemie und Biochemie, Takustrasse 3, D-14195 Berlin, Germany 10.3762/bjoc.12.289 Abstract Iodination of carbohydrate-derived 3,6-dihydro-2H-1,2-oxazines of type 3 using iodine and

• studied syntheses and applications of 3,6-dihydro-2H-1,2-oxazines of type 3 [1][2]. These N,O-heterocycles are easily prepared in enantiopure form by a stereodivergent [3 + 3] cyclization of carbohydrate-derived nitrones 2 and lithiated alkoxyallenes 1 (Scheme 1) [3][4]. Subsequently we investigated

• -alkoxy-γ-amino-aldehydes and ketones [14]. In this context, a series of publications of our group reported on syntheses of carbohydrate mimetics [15][16][17][18][19][20] that are based on aminopyrans, aminooxepanes or other aminopolyols and that were examined for example as ligands of L- and P-selectin

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

• carbohydrate epitopes with O-alkylated ring hydroxy groups. In this context, we report the first synthesis of an O-methylated selenoglycoside, specifically methyl 2-O-methyl-L-selenofucopyranoside, a ligand of the lectin tectonin-2 from the mushroom Laccaria bicolor. The synthetic route required a strategic

• : carbohydrate chemistry; fucose; lectin; selenoglycoside; Introduction Since the discovery of seleno mercaptan by Siemens in 1847 [1], organoselenium compounds have attracted high attention. Besides their biological and pharmaceutical relevance, e.g., selenocysteine or ebselen [2][3][4][5], selenium-containing

• complex with selenium-containing ligands can enable the phase determination without the need for recombinant incorporation of amino acid analogues. Buts et al. first reported the use of a selenoglycoside as ligand for a carbohydrate-binding protein, and its use for X-ray crystallographic structure

Orthogonal protection of saccharide polyols through solvent-free one-pot sequences based on regioselective silylations

• Serena Traboni,
• Emiliano Bedini and
• Alfonso Iadonisi

Beilstein J. Org. Chem. 2016, 12, 2748–2756, doi:10.3762/bjoc.12.271

• ), although, as shown earlier in Table 2, entry 4, direct silylation of the same precursor was quite unfruitful. Conclusion In the first part of this paper we have introduced a very simple approach to carry out the selective TBDMS or TBDPS protection of carbohydrate polyols taking advantage of reactions

Benzothiadiazole oligoene fatty acids: fluorescent dyes with large Stokes shifts

• Lukas J. Patalag and
• Daniel B. Werz

Beilstein J. Org. Chem. 2016, 12, 2739–2747, doi:10.3762/bjoc.12.270

• as the carbohydrate part of glycolipids [7][8]. A further alternative is to render the lipid and especially the fatty acid part fluorescently active by the introduction of fluorescent moieties (Figure 1). Prominent examples in this area are NBD- (nitrobenzoxadiazole) [9][10], BODIPY- (boron

Enzymatic synthesis and phosphorolysis of 4(2)-thioxo- and 6(5)-azapyrimidine nucleosides by E. coli nucleoside phosphorylases

• Vladimir A. Stepchenko,
• Anatoly I. Miroshnikov,
• Frank Seela and
• Igor A. Mikhailopulo

Beilstein J. Org. Chem. 2016, 12, 2588–2601, doi:10.3762/bjoc.12.254

• transglycosylation reaction of the corresponding thioxopyrimidines employing thymidine as a donor of the carbohydrate residue and E. coli TP as a biocatalyst [35]; 6-azauracil (3a) and 6-azathymine (4a) displayed no substrate activity in analogous reactions (cf. [26][27][28][29]). These studies prompted us to

Efficient mechanochemical synthesis of regioselective persubstituted cyclodextrins

• Laszlo Jicsinszky,
• Marina Caporaso,
• Katia Martina,
• Emanuela Calcio Gaudino and
• Giancarlo Cravotto

Beilstein J. Org. Chem. 2016, 12, 2364–2371, doi:10.3762/bjoc.12.230

• simplicity and flexibility [18][19][20][21]. While the mechanochemical manipulation of covalent bonds is hardly a brand new concept, its diffusion into carbohydrate chemistry, and particularly into CD derivatization, has been rather slow [22][23]. The ability of HEBM to favour the nucleophilic substitution

Useful access to enantiomerically pure protected inositols from carbohydrates: the aldohexos-5-uloses route

• Felicia D’Andrea,
• Giorgio Catelani,
• Lorenzo Guazzelli and
• Venerando Pistarà

Beilstein J. Org. Chem. 2016, 12, 2343–2350, doi:10.3762/bjoc.12.227

• the stereoselective synthesis of enantiopure inositol derivatives, also the possibility to pick and tag specific positions of the inositol ring, installing the protective groups earlier on the carbohydrate frame through the well-known sugar chemistry, is of extreme interest. Although some attractive

Isosorbide and dimethyl carbonate: a green match

• Fabio Aricò and
• Pietro Tundo

Beilstein J. Org. Chem. 2016, 12, 2256–2266, doi:10.3762/bjoc.12.218

• reactivity of isosorbide and the non-toxic properties of DMC represent indeed a green match leading to several industrial appealing potential applications. Keywords: carbohydrate chemistry; D-sorbitol; dimethyl carbonate; green chemistry; isosorbide; Review Introduction In the last twenty years biorefinery

Superelectrophilic activation of 5-hydroxymethylfurfural and 2,5-diformylfuran: organic synthesis based on biomass-derived products

• Dmitry S. Ryabukhin,
• Dmitry N. Zakusilo,
• Mikhail O. Kompanets,
• Anton A.Tarakanov,
• Irina A. Boyarskaya,
• Tatiana O. Artamonova,
• Mikhail A. Khohodorkovskiy,
• Iosyp O. Opeida and
• Aleksander V. Vasilyev

Beilstein J. Org. Chem. 2016, 12, 2125–2135, doi:10.3762/bjoc.12.202

• ; Introduction Nowadays great attention is paid to the use of renewable resources for obtaining fine chemicals and fuels (see numerous reviews [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16]). The biorefinery of renewable lignin-carbohydrate materials affords various low-molecular weight organic

The direct oxidative diene cyclization and related reactions in natural product synthesis

• Juliane Adrian,
• Leona J. Gross and
• Christian B. W. Stark

Beilstein J. Org. Chem. 2016, 12, 2104–2123, doi:10.3762/bjoc.12.200

• (6) (Scheme 4). It was also possible to produce another carbohydrate using the same synthetic pathway. Thus, mono-protection of THF diol 5 followed by oxidation of the remaining free primary hydroxy group to the carboxylic acid and a final hydrogenolysis gave (+)-D-chitaric acid (7) with a yield of

p-Nitrophenyl carbonate promoted ring-opening reactions of DBU and DBN affording lactam carbamates

• Madhuri Vangala and
• Ganesh P Shinde

Beilstein J. Org. Chem. 2016, 12, 2086–2092, doi:10.3762/bjoc.12.197

• carbohydrate–protein interactions [25], ligation and surfactant properties [26][27]. Although p-nitrophenyl carbonates were extensively utilized in these reactions, the nucleophilicity of amidine bases towards these carbonates was not encountered so far. In continuation of our interest in carbohydrates [28][29

Stereo- and regioselectivity of the hetero-Diels–Alder reaction of nitroso derivatives with conjugated dienes

• Lucie Brulíková,
• Aidan Harrison,
• Marvin J. Miller and
• Jan Hlaváč

Beilstein J. Org. Chem. 2016, 12, 1949–1980, doi:10.3762/bjoc.12.184

• Asymmetric (chiral) hetero-Diels–Alder reactions in a stereoselective (enantioselective or diastereoselective) manner have become very popular in the last decade. Pioneering works by Kresze and Vasella [56][94][105] using carbohydrate-based α-chloronitroso agents and Kirby [14] using acylnitroso compounds

Synthesis and NMR studies of malonyl-linked glycoconjugates of N-(2-aminoethyl)glycine. Building blocks for the construction of combinatorial glycopeptide libraries

• Markus Nörrlinger,
• Sven Hafner and
• Thomas Ziegler

Beilstein J. Org. Chem. 2016, 12, 1939–1948, doi:10.3762/bjoc.12.183

• , investigating the delicate carbohydrate–protein interactions on a molecular level is an inalienable prerequisite for a deep understanding of the fundamental cellular recognition processes involving the complex saccharides of the glycocalyx [5][6][7][8]. Unfortunately, isolation of pure carbohydrate material or