- Chemical synthesis and pharmacological properties of heparin pentasaccharide analogues
-
The pentasaccharide fondaparinux is a synthetic anticoagulant based on heparin antithrombin-binding sequence. Fondaparinux improves safety and predictable pharmacodynamics compared with heparins; however, it requires a complicate synthesis process which contain more than 50 steps of synthesis. Herein, we designed and synthesized four fondaparinux analogues (compounds 1, 2, 3, 4) using a [2+3] convergent synthetic method, which greatly simplified the synthetic process, improved the product yield, and curtailed the expenditures. These synthesized compounds showed stronger anticoagulant activities by factor Xa inhibition (IC50 725–1126 nM vs. 1909 nM for fondaparinux) in the AT-dependent manner. After subcutaneous (s.c.) administration to rats, the compounds displayed long-lasting anti-factor Xa activities and inhibition of thrombin generation ex vivo. Compared with fondaparinux, these compounds were slowly eliminated after s.c. administration to rats, the half-lies (t1/2) were more than 2-fold of that of fondaparinux. These results suggested the pentasaccharide analogues may exhibit better pharmacokinetic and predictable pharmacodynamic characteristics.
- Luo, Lan,Wu, Jian,Wu, Mingyi,Wu, Xin,Xu, Dan,Zhang, Linlin,Zhou, Zhipeng
-
-
- Chemoenzymatic Synthesis of Sialosides Containing 7- N- or 7,9-Di- N-acetyl Sialic Acid as Stable O-Acetyl Analogues for Probing Sialic Acid-Binding Proteins
-
A novel chemoenzymatic synthon strategy has been developed to construct a comprehensive library of α2-3- and α2-6-linked sialosides containing 7-N- or 7,9-di-N-acetyl sialic acid, the stable analogue of naturally occurring 7-O-acetyl- or 7,9-di-O-acetyl-s
- Chen, Xi,Diaz, Sandra,Kooner, Anoopjit Singh,Santra, Abhishek,Varki, Ajit,Yu, Hai
-
p. 14381 - 14397
(2021/11/01)
-
- Synthesis and conformational analysis of vicinally branched trisaccharide β-d-Galf-(1 → 2)-[β-d-Galf-(1 → 3)-]-α-GalpfromCryptococcus neoformansgalactoxylomannan
-
The synthesis of a vicinally branched trisaccharide composed of twod-galactofuranoside residues attachedviaβ-(1 → 2)- and β-(1 → 3)-linkages to the α-d-galactopyranoside unit has been performed for the first time. The reported trisaccharide represents the galactoxylomannan moiety first described in 2017, which is the capsular polysaccharide of the opportunistic fungal pathogenCryptococcus neoformansresponsible for life-threatening infections in immunocompromised patients. The NMR-data reported here for the synthetic model trisaccharide are in good agreement with the previously assessed structure of galactoxylomannan and are useful for structural analysis of related polysaccharides. The target trisaccharide as well as the constituent disaccharides were analyzed by a combination of computational and NMR methods to demonstrate good convergence of the theoretical and experimental results. The results suggest that the furanoside ring conformation may strongly depend on the aglycon structure. The reported conformational tendencies are important for further analysis of carbohydrate-protein interaction, which is critical for the host response towardC. neoformansinfection.
- Dorokhova, Vera S.,Gerbst, Alexey G.,Komarova, Bozhena S.,Previato, José O.,Previato, Lúcia Mendon?a,Dmitrenok, Andrey S.,Shashkov, Alexander S.,Krylov, Vadim B.,Nifantiev, Nikolay E.
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supporting information
p. 2923 - 2931
(2021/04/14)
-
- Synthesis of nature product kinsenoside analogues with anti-inflammatory activity
-
Kinsenoside is the major bioactive component from herbal medicine with a broad range of pharmacological functions. Goodyeroside A, an epimer of kinsenoside, remains less explored. In this report we chemically synthesized kinsenoside, goodyeroside A and their analogues with glycan variation, chirality inversion at chiral center(s), and bioisosteric replacement of lactone with lactam. Among these compounds, goodyeroside A and its mannosyl counterpart demonstrated superior anti-inflammatory efficacy. Furthermore, goodyeroside A was found to suppresses inflammatory through inhibiting NF-κB signal pathway, effectively. Structure-activity relationship is also explored for further development of more promising kinsenoside analogues as drug candidates.
- Song, Wei,Sun, Yong,Xu, Lintao,Sun, Yajing,Li, Tianlu,Peng, Peng,Lou, Hongxiang
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supporting information
(2020/12/02)
-
- Solvent-Free Glycosylation from per-O-Acylated Donors Catalyzed by Methanesulfonic Acid
-
The huge importance of carbohydrates and their derivatives in biomedical and industrial applications call for the development of streamlined and sustainable procedures for their synthetic elaboration. Here reported a novel glycosylation method based on direct activation of readily available per-O-acylated (acetylated or benzoylated) donors, promoted under air by methanesulfonic acid as a cheap and green catalyst in the absence of any solvent. Besides the beneficial avoidance of toxic and polluting organic solvents, these conditions were found critical for activating such poorly reactive donors with a very small catalyst loading (only 5 mol %), instead of stoichiometric Lewis acid promoters typically employed. Desired glycosides were quickly obtained, in most cases with high 1,2-trans stereoselectivity. Other main advantages over reported glycosylations with similar donors are the limited stoichiometric excess of the acceptor (or the donor), the easy applicability and low cost of the procedure and the wide target scope, also covering the synthesis of disaccharides and other non-trivial glycosides with applicable potential.
- Bedini, Emiliano,Iadonisi, Alfonso,Silipo, Alba,Traboni, Serena,Vessella, Giulia
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p. 5669 - 5676
(2021/11/11)
-
- Studies towards the total synthesis of repeating unit of O-sulfated polysaccharide from marine bacterium Cobetia pacifica KMM 3878
-
Herein we report assembly of the appropriately protected trisaccharide repeating unit of Cobetia pacifica KMM 3878 O-sulfated polysaccharide. Our synthesis involves 3,4-O-pyruvilated galactose as the key building block which acts as a donor as well as acceptor in the construction of trisaccharide. We obtained the R isomer as a major stereoisomer in the pyruvilation reaction. The glycosylations proceeded with high stereo and regioselectivity.
- Pradhan, Kabita,Podilapu, Ananda Rao,Kulkarni, Suvarn S.
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p. 255 - 264
(2020/03/18)
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- Scope of the DMC mediated glycosylation of unprotected sugars with phenols in aqueous solution
-
Activation of reducing sugars in aqueous solution using 2-chloro-1,3-dimethylimidazolinium chloride (DMC) and triethylamine in the presence of para-nitrophenol allows direct stereoselective conversion to the corresponding 1,2-Trans para-nitrophenyl glycosides without the need for any protecting groups. The reaction is applicable to sulfated and phosphorylated sugars, but not to ketoses or uronic acids or their derivatives. When applied to other phenols the product yield was found to depend on the pKa of the added phenol, and the process was less widely applicable to 2-Acetamido sugars. For 2-Acetamido substrates an alternative procedure in which the glycosyl oxazoline was pre-formed, the reaction mixture freeze-dried, and the crude product then reacted with an added phenol in a polar aprotic solvent system with microwave irradiation proved to be a useful simplification.
- Fairbanks, Antony J.,Qiu, Xin
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p. 7355 - 7365
(2020/10/13)
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- Regio/Stereoselective Glycosylation of Diol and Polyol Acceptors in Efficient Synthesis of Neu5Ac-α-2,3-LacNPhth Trisaccharide
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A concise approach to a Neu5Ac-α-2,3-LacNPhth trisaccharide derivative was developed. First, the regio/stereoselective glycosylation between glycoside donors and glucoNPhth diol acceptors was investigated. It was found that the regioselectivity depends not only on the steric hindrance of the C2-NPhth group and the C6-OH protecting group of the glucosamine acceptors, but also on the leaving group and protecting group of the glycoside donors. Under optimized conditions, LacNPhth derivatives were synthesized in up to 92 % yield through a regio/stereoselective glycosylation between peracetylated-α-galactopyranosyl trichloroacetimidate and p-methoxyphenyl 6-O-tert-butyldiphenylsilyl-2-deoxy-2-phthalimido-β-d-glucopyranoside, avoiding the formation of glycosylated orthoesters and anomeric aglycon transfer. Then, the LacNPhth derivative was deacylated and then protected on the primary position by TBDPS to form a LacNPhth polyol acceptor. Finally, the Neu5Ac-α-2,3-LacNPhth derivative was synthesized in 48 % yield through the regio/stereoselective glycosylation between the LacNPhth polyol acceptor and a sialyl phosphite donor. Starting from d-glucosamine hydrochloride, the target Neu5Ac-α-2,3-LacNPhth derivative was synthesized in a total yield of 18.5 % over only 10 steps.
- Zhang, Ying,Zhao, Fu-Long,Luo, Tao,Pei, Zhichao,Dong, Hai
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supporting information
p. 223 - 234
(2018/12/05)
-
- The use of the novel glycosyl acceptor and supramer analysis in the synthesis of sialyl-α(2–3)-galactose building block
-
A new glycosyl acceptor to be used in sialylation was designed as a 3-hydroxy derivative of 4-methoxyphenyl β-D-galactopyranoside with 2-O-acetyl group and O-4 and O-6 protected as benzylidene acetal. Two alternative syntheses of this compound were compar
- Nagornaya, Marina O.,Orlova, Anna V.,Stepanova, Elena V.,Zinin, Alexander I.,Laptinskaya, Tatiana V.,Kononov, Leonid O.
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-
- N-ACETYLATED SIALIC ACIDS AND RELATED SIALOSIDES
-
The present invention provides N-acetyl derivatives of sialic acids, including N-acetyl derivatives of Neu5Ac and Neu5Gc. Methods for preparing related precursors and a variety of sialosides are also disclosed.
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- Rapid phenolic O-glycosylation of small molecules and complex unprotected peptides in aqueous solvent
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Glycosylated natural products and synthetic glycopeptides represent a significant and growing source of biochemical probes and therapeutic agents. However, methods that enable the aqueous glycosylation of endogenous amino acid functionality in peptides without the use of protecting groups are scarce. Here, we report a transformation that facilitates the efficient aqueous O-glycosylation of phenolic functionality in a wide range of small molecules, unprotected tyrosine, and tyrosine residues embedded within a range of complex, fully unprotected peptides. The transformation, which uses glycosyl fluoride donors and is promoted by Ca(OH)2, proceeds rapidly at room temperature in water, with good yields and selective formation of unique anomeric products depending on the stereochemistry of the glycosyl donor. High functional group tolerance is observed, and the phenol glycosylation occurs selectively in the presence of virtually all side chains of the proteinogenic amino acids with the singular exception of Cys. This method offers a highly selective, efficient, and operationally simple approach for the protecting-group-free synthesis of O-aryl glycosides and Tyr-O-glycosylated peptides in water.
- Wadzinski, Tyler J.,Steinauer, Angela,Hie, Liana,Pelletier, Guillaume,Schepartz, Alanna,Miller, Scott J.
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p. 644 - 652
(2018/05/04)
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- A new look at acid catalyzed deacetylation of carbohydrates: A regioselective synthesis and reactivity of 2-O-acetyl aryl glycopyranosides
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In the present work we report that acetyl groups of per – acetylated aryl glycosides have different reactivity during the acidic deacetylation using HCl/EtOH in CHCl3, which leads to preferential deacetylation at O-3, O-4 and O-6. Thereby, the one-step preparation of 2-O-acetyl aryl glycosides with simple aglycon was accomplished for the first time. It was proved that the found reagent is to be general and unique for the preparation of series of 2-О-acetyl aryl glycosides. We have determined the influence of both carbohydrate moiety and the aglycon on the selectivity of deacetylation reaction by kinetic experiments. Using DFT/B3LYP/6-31G(d,p) and semi-empirical АМ1 methods we have found that the highest activation barrier is for 2-О-acetyl group. This completely explains the least reactivity of 2-О-acetyl group.
- Stepanova, Elena V.,Nagornaya, Marina O.,Filimonov, Victor D.,Valiev, Rashid R.,Belyanin, Maxim L.,Drozdova, Anna K.,Cherepanov, Victor N.
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-
- Total Synthesis of the Diglycosidic Tetramic Acid Ancorinoside A
-
Ancorinoside A, a metabolite of a sponge Ancorina sp., was prepared in 18 steps as the first derivative of this class of glycosylated 3-acyltetramic acids. It features a β-d-glucopyranosyl-(1→4)-β-d-galacturonic acid linked to a d-aspartic acid derived te
- Petermichl, Markus,Schobert, Rainer
-
supporting information
p. 14743 - 14746
(2017/10/27)
-
- SGLT-2 INHIBITORS
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Provided are compounds of SGLT-2 inhibitors, pharmaceutically acceptable salts, hydrides and stereoisomers thereof. The compounds are employed in pharmaceutical compositions, and methods of making and use, including treating a person in need thereof with
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-
Paragraph 0159; 0161
(2016/04/09)
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- HUMAN iNKT CELL ACTIVATION USING GLYCOLIPIDS
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Glycosphingolipids (GSLs) compositions and methods for iNKT-independent induction of chemokines are disclosed.
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-
Paragraph 0269
(2016/05/10)
-
- Stereocontrolled Synthesis of Phenolic α-d-Glycopyranosides
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Adopting the ‘remote activation concept’ toward stereocontrolled glycoside synthesis with minimal use of protection groups, a general synthesis of phenolic 1,2-cis glycopyranosides is reported, as exemplified by aryl α-d-galacto-, α-d-gluco- and 2-azido α-d-glucopyranosides among others using glycosyl donors bearing an anomeric (3-bromo-2-pyridyloxy) group and catalyzed by methyl triflate.
- St-Pierre, Gabrielle,Dafik, Laila,Klegraf, Ellen,Hanessian, Stephen
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supporting information
p. 3575 - 3588
(2016/10/17)
-
- HUMAN iNKT CELL ACTIVATION USING GLYCOLIPIDS WITH ALTERED GLYCOSYL GROUPS
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Glycosphingolipids (GSLs) bearing α-glucose (α-Glc) that preferentially stimulate human invariant NKT (iNKT) cells are provided. GSLs with α-glucose (α-Glc) that exhibit stronger induction in humans (but weaker in mice) of cytokines and chemokines and exp
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-
Paragraph 0288; 0291; 0292; 0314
(2015/03/16)
-
- Total Synthesis and Biological Evaluation of Ipomoeassin F and Its Unnatural 11R-Epimer
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Ipomoeassin F, a macrolide glycoresin containing an embedded disaccharide, possesses potent in vitro antitumor activity with an unknown mechanism of function. It inhibits tumor cell growth with single-digit nanomolar IC50 values, superior to many clinical chemotherapeutic drugs. To facilitate translation of its bioactivity into protein function for drug development, we report here a new synthesis for the gram-scale production of ipomoeassin F (3.8% over 17 linear steps) from commercially available starting materials. The conformation-controlled subtle reactivity differences of the hydroxyl groups in carbohydrates were utilized to quickly construct the disaccharide core, which, along with judicial selection of protecting groups, made the current synthesis very efficient. The same strategy was also applied to the smooth preparation of the 11R-epimer of ipomoeassin F for the first time. Cytotoxicity assays demonstrated the crucial role of the natural 11S configuration. In addition, cell cycle analyses and apoptosis assays on ipomoeassin F and/or its epimer were conducted. This work has laid a solid foundation for understanding the medicinal potential of the ipomoeassin family of glycolipids in the future.
- Zong, Guanghui,Barber, Eric,Aljewari, Hazim,Zhou, Jianhong,Hu, Zhijian,Du, Yuchun,Shi, Wei Q.
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p. 9279 - 9291
(2015/09/28)
-
- Identification of living legionella pneumophila using species-specific metabolic lipopolysaccharide labeling
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Legionella pneumophila is a pathogenic bacterium involved in regular outbreaks characterized by a relatively high fatality rate and an important societal impact. Frequent monitoring of the presence of this bacterium in environmental water samples is neces
- Pons, Jordi Mas,Dumont, Audrey,Sautejeau, Gregory,Fugier, Emilie,Baron, Aurelie,Dukan,Vauzeilles, Boris
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supporting information
p. 1275 - 1278
(2014/03/21)
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- Neighbouring group participation during glycosylation: Do 2-substituted ethyl ethers participate?
-
The development of new protecting groups that undergo neighbouring group participation (NGP) via six-membered ring intermediates to promote the formation of α-1,2-cis glycosidic linkages complements the established use of 5-ring NGP in terms of stereochem
- Cox, Daniel J.,Singh, Govind P.,Watson, Andrew J. A.,Fairbanks, Antony J.
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p. 4624 - 4642
(2014/08/05)
-
- Tuning the moenomycin pharmacophore to enable discovery of bacterial cell wall synthesis inhibitors
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New antibiotic drugs need to be identified to address rapidly developing resistance of bacterial pathogens to common antibiotics. The natural antibiotic moenomycin A is the prototype for compounds that bind to bacterial peptidoglycan glycosyltransferases
- Gampe, Christian M.,Tsukamoto, Hirokazu,Doud, Emma H.,Walker, Suzanne,Kahne, Daniel
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p. 3776 - 3779
(2013/04/23)
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- A divergent approach to the synthesis of simplexides and congeners via a late-stage olefin cross-metathesis reaction
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Simplexides constitute a unique group of immunosuppressive glycolipids that demonstrate antiproliferative activities against activated T-cell lymphocytes via a unique non-cytotoxic inhibition. To investigate the structure-activity relationship of the varied long-chain secondary alcohols on simplexides, we developed an efficient and divergent route to the synthesis of simplexides and congeners, taking advantage of a late-stage olefin cross-metathesis reaction.
- Li, Jiakun,Li, Wei,Yu, Biao
-
supporting information
p. 4971 - 4974
(2013/08/23)
-
- Synthesis and immunological characterization of modified hyaluronic acid hexasaccharide conjugates
-
The synthesis of a tetanus toxoid (TT)-conjugate of a hyaluronic acid (HA) hexasaccharide is described. The compound was intended for use in monitoring HA levels as a disease marker and as a potential vaccine against Group A Streptococcus (GAS) infections. We also report the synthesis of a chemically modified HA-hexasaccharide-TT conjugate in which the N-acetyl moiety of the N-acetyl-d-glucosamine residue is replaced with an N-propionyl unit in order to enhance immunogenicity. The oligosaccharides are synthesized in a convergent manner. The TT-conjugate syntheses rely on the reaction of the amines on the 6-aminohexyl aglycon of the hexasaccharides with diethyl squarate to give the monoethyl squarate adducts. Subsequent reactions with lysine ε-amino groups on TT then give the glycoconjugates containing an average of 8 hexasaccharide haptens per TT molecule. Immunological studies in mice show very similar antibody responses with both conjugates, suggesting that the N-acetyl groups of the glucosaminyl residues of the HA-hexasaccharide are not a critical part of the epitope recognized by the anti-HA polyclonal immune response. Furthermore, it would appear that the N-acyl moieties are not in close contact with the amino acid residues of the antibody combining sites.
- Gu, Guofeng,Adabala, Pal John Pal,Szczepina, Monica G.,Borrelli, Silvia,Pinto, B. Mario
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p. 8004 - 8019
(2013/09/12)
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- 2,6-Disubstituted benzoates as neighboring groups for enhanced diastereoselectivity in β-galactosylation reactions: Synthesis of β-1,3-linked oligogalactosides related to arabinogalactan proteins
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(Chemical Equation Presented) Arabinogalactan proteins (AGPs) are plant glycoproteins which contain a β-1,3-linked galactan core. The synthesis of the β-galactopyranose-1,3-β-galactopyranose linkage using various 2-O-acyl-protected glycosyl donors has bee
- McGill, Nathan W.,Williams, Spencer J.
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experimental part
p. 9388 - 9398
(2010/03/04)
-
- MOENOMYCIN ANALOGS, METHODS OF SYNTHESIS, AND USES THEREOF
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The present invention provides novel moenomycin analogs as well as pharmaceutical compositions thereof, methods of synthesis, and methods of use in treating an infection by administering an inventive compound to a subject in need thereof. The moenomycin a
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- Synthesis of Neu5Ac-Gal-functionalized gold glyconanoparticles
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Neu5Ac-Gal-containing neoglycoside 1 was convergently synthesized through Cu(I)-catalyzed 1,3-dipolar cycloaddition of methyl (6-azidohexyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-2-O-α-d-glycero-d-galacto-2-nonulopyranosyl)uronate and 11-thioacety
- Zhang, Lei,Wei, Guohua,Du, Yuguo
-
experimental part
p. 2083 - 2087
(2010/03/01)
-
- A Chemoenzymatic route to conjugatable β(1→3)-Glucan Oligosaccharides
-
3II-O-Allyl-α laminaribiosyl fluoride was prepared as a key synthon for the enzymatic synthesis of β(1→3)-glucan oligosaccharides, catalyzed by a mutated β(1→3)-glucanase (E231G) from barley (Hordeum vulgare L.). A strategy was developed for en
- Montel, Emilie,Hrmova, Maria,Fincher, Geoffrey B.,Driguez, Hugues,Cottaz, Sylvain
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experimental part
p. 575 - 584
(2010/01/16)
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- CARBOHYDRATE BASED TOLL-LIKE RECEPTOR (TLR) ANTAGONISTS
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The invention provides carbohydrate based compounds, methods of preparation, and compositions useful for modulating signaling through Toll-like receptors. The methods involve contacting a TLR-expressing cell with a carbohydrate based compound of the inven
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Page/Page column 19
(2009/09/07)
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- Concise synthesis of two pentasaccharides corresponding to the α-chain oligosaccharides of Neisseria gonorrhoeae and Neisseria meningitidis
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Two pentasaccharides containing a common tetrasaccharide (lacto-N-neotetraose) core, and d-galactosamine and N-acetyl neuraminic acid in the non-reducing ends, respectively, corresponding to the lipooligosaccharides of Neisseria gonorrhoeae and Neisseria
- Mandal, Pintu Kumar,Misra, Anup Kumar
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p. 8685 - 8691
(2008/12/21)
-
- Towards oligosaccharide library synthesis by fluorous mixture method
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The synthesis of an oligosaccharide library by a fluorous tag method is reported here. Several acceptors and donors were mixed and glycosylated. The reaction mixture was purified by chromatography over fluorous HPLC to provide disaccharides in order of increasing fluorine content of the tag. This method could be applied to oligosaccharide libraries consisting of two sets of structural isomers.
- Tojino, Mami,Mizuno, Mamoru
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supporting information; body text
p. 5920 - 5923
(2009/04/05)
-
- Synergistic solvent effect in 1,2-cis-glycoside formation
-
Construction of three continuous 1,2-cis-α-glucosidic linkages was achieved in optimized solvent system. High-throughput optimization was conducted, by using substrates protected by perdeuterated benzyl (Bn-d7) groups. It enabled facile evaluat
- Ishiwata, Akihiro,Munemura, Yuichi,Ito, Yukishige
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-
- Synthesis of a C-linked hyaluronic acid disaccharide mimetic
-
The synthesis of a C-disaccharide that is designed as a mimetic for the repeating unit disaccharide of hyaluronic acid is described. The target compound was obtained via the SmI2-promoted coupling reaction of the sulfone, 2-acetamido-4,6-O-benz
- Ren, Zhong-Xu,Yang, Qiang,Price, Kenneth N.,Chen, Tianniu,Nygren, Cara,Turner, John F.C.,Baker, David C.
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p. 1668 - 1679
(2008/03/11)
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- Urinary excretion of arbutin metabolites after oral administration of bearberry leaf extracts
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An HPLC assay with fluorimetric detection of the arbutin metabolites hydroquinone glucuronide (2) and hydroquinone sulphate (6) in urine was developed and validated. Methylarbutin (4) and 6 were synthesised as reference substances. Compound 2 was prepared enzymatically from hydroquinone and uridine 5-diphosphoglucuronic acid using the glucosyltransferase system of rat liver microsomes and enriched by two liquid-liquid and an additional solid phase extraction. Compound 2 as the main component of this purified product was identified by UV and fluorescence spectroscopy, by HPLC-MS, and by enzymatic hydrolysis to hydroquinone (5). The assay yields precise and accurate urine levels of 2, 5 and 6 in the concentration range expected after oral administration of recommended therapeutic doses of bearberry leaf extract. In a preliminary pharmacokinetic study on 3 volunteers the time-dependent renal excretion of arbutin metabolites 2, 5 and 6 was investigated after ingestion of an aqueous bearberry leaf extract containing an arbutin dose recommended by the German Kommission E. More than half of the administered dose of arbutin was excreted within 4 hours mainly in form of the metabolites 2 and 6 and more than 75% of the total applied arbutin was excreted within 24 h. The elimination of 5 was negligible in 2 out of 3 volunteers. The excretion of this metabolite in the third test person reached 5.6% of the total administered arbutin dose. The preliminary pharmacokinetic results confirm that renal elimination of toxicologically critical concentrations of the metabolite 5 will not be expected.
- Quintus, Joachim,Kovar, Karl-Artur,Link, Peter,Hamacher, Harald
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p. 147 - 152
(2007/10/03)
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- Synthesis of some blocked di- and trisaccharide derivatives related to the repeating unit of the O-antigen from Shigella dysenteriae type 3 in the form of their glycosides
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Starting from D-galactose and D-galactosamine hydrochloride, two new monosaccharide synthons namely 2-(trimethylsilyl)ethyl 4-O-acetyl-2,6-di-O- benzyl-β-D-galactopyranoside 2 and phenyl 3-O-acetyl-4,6-O-benzylidene-2- deoxy-2-phthalimido-1-thio-β-D-galac
- Sarkar, Sujit Kumar,Roy, Nirmolendu
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p. 2386 - 2394
(2007/10/03)
-
- Syntheses of arabinogalactans consisting of β-(1 → 6)-linked D-galactopyranosyl backbone and α-(1 → 3)-linked L-arabinofuranosyl side chains
-
Two arabinogalactosyl nonasaccharides, β-D-Galp-(1→6)-[α-L- Araf-(1→3)]-β-D-Galp-(1→6)-β-D-Galp-(1→6) -β-D-Galp-(1→6)-[α-L-Araf-(1→5)-α-L-Araf-(1→3)] -β-D-Galp-(1→6)-β-D-Galp and β-D-Galp-(1→6)-[α-L- Araf-(1→5)-α-L-Araf-(1→3)]-β-D-Galp-(1→6) -β-D-Galp-(1→
- Li, Aixiao,Kong, Fanzuo
-
p. 1847 - 1856
(2007/10/03)
-
- Efficient synthesis of two HNK-1 related pentasaccharides
-
Two pentasaccharides, representative of those found on complex N-glycans, were synthesized for use as potential substrates for sulfotransferases. The synthesis was achieved by the addition of a disaccharide donor β-D-GlcA(1→3)α-D-Gal-trichloroacetimidate
- Belot, Frederic,Otter, Albin,Fukuda, Minoru,Hindsgaul, Ole
-
p. 1315 - 1318
(2007/10/03)
-
- A practical synthesis of β-D-GlcA-(1→3)-β-D-Gal-(1→3)-β-D-Gal-(1→4)-D- Xyl, a part of the common linkage region of a glycosaminoglycan
-
A practical synthesis of β-D-GlcA-(1→3)-β-D-Gal-(1→3)-β-D-Gal-(1→4)- β-D-Xyl-(1→OMe) was achieved by coupling of methyl 2,3,4-tri-O-acetyl-α-D-glucopyranosyluronate trichloroacetimidate with a trisaccharide acceptor. The trisaccharide acceptor was obtained by condensation of 3-O-allyl-2,4,6-tri-O-benzoyl-β-D-galactopyranosyl-(1→3)-2,4,6- tri-O-benzoyl-α-D-galactopyranosyl trichloroacetimidate with methyl 2,3-di-O-benzoyl-β-D-xylopyranoside, followed by deallylation. The β-(1→3)-linked disaccharide was prepared readily with p-methoxyphenyl 3-O-allyl-2,4,6-tri-O-benzoyl-β-D-galactopyranoside as the key synthon. The α-(1→3)-linkage was formed in considerable amount with galactose mono- and disaccharide trichloroacetimidate donors with C-2 neighboring group participation.
- Chen, Langqiu,Kong, Fanzuo
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p. 1373 - 1380
(2007/10/03)
-
- Aflexible synthesis of cyclopentitol derivatives based on ring-closing metathesis of carbohydrate-derived 1,6-dienes
-
Four partially protected stereoisomeric cyclopentenetriols 5, 10, 15 and 21 have been prepared by ring-closing metathesis of carbohydrate-derived 1,6-dienes. The presence of a differentiated allylic alcohol in the cyclopentenetriols allows a variety of synthetic transformations, underlining the synthetic use of the prepared cyclopentenetriol derivatives as chiral building blocks.
- Ovaa, Huib,Lastdrager, Bas,Codee, Jeroen D. C.,Van der Marel, Gijs A.,Overkleeft, Herman S.,Van Boom, Jacques H.
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p. 2370 - 2377
(2007/10/03)
-
- Process for the preparation of tetrahydropyran derivatives
-
A process of making arbutin and its derivatives comprises solvolyzing an acylated precursor of arbutin or its derivative in a solution comprising an organic solvent and a base, neutralizing the solution with an acid, and crystillizing the product arbutin or its derivative. The process may be employed on an industrial scale and avoids the use of ion exchange columns. The process has the advantages of not requiring ion exchange columns and peripheral devices, which leads to cost and time savings, due to the elimination of column regeneration steps. Waste water from column regeneration is also eliminated.
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- Synthesis of a divalent glycoside of an α-galactosyl disaccharide epitope involved in the hyperacute rejection of xenotransplantation
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3,6-Dioxaoct-1,8-diyl di-(3-O-α-D-galactopyranosyl-β-D-galactopyranoside) was synthesized for use in research on hyperacute rejection of xenotransplantation. The trichloroacetate method was successfully applied to form stereoselectively the α-D-galactosyl
- Lu, Yi-Pin,Li, Hui,Cai, Meng-Shen,Li, Zhong-Jun
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p. 289 - 294
(2007/10/03)
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- Galabiosyl donors; efficient synthesis from 1,2,3,4,6-penta-O-acetyl-β-D-galactopyranose
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1,2,3,4,6-Penta-O-acetyl-β-D-galactopyranose was transformed into phenyl 2,3,4,6-tetra-O-benzyl-1-thio-β-D-galactopyranoside (5) and 4-methoxyphenyl 2,3,6-tri-O-benzoyl-β-D-galactopyranoside (8) in 73% (two steps) and 58% (three steps) yield, respectively. Glycosylation of the acceptor 8 with donor 5 using N-iodosuccinimide-trimethylsilyl trifluoromethanesulfonate as promoter furnished the galabioside 9 (8.8 g) in 95% yield. Further transformations provided in high yields anomerically-activated galabiosides (thioglycoside (1), trichloroacetimidate (2), and bromosugar (3)) suitable for use as glycosyl donors in syntheses of galabiose-containing oligosaccharides. Several of the compounds reported here are crystalline, which greatly simplified purifications. (C) 2000 Elsevier Science Ltd.
- Ohlsson, Joergen,Magnusson, Goeran
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- Efficient Synthesis of 3,6-Dideoxy-β-D-arabino-hexopyranosyl-Terminated LacdiNac Glycan Chains of the Trichinella spiralis Parasite
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The synthesis of a linear trisaccharide epitope of the Trichinella spiralis N-linked glycan, in a form amenable to glycoconjugate formation, is reported. The trisaccharide contains the synthetically challenging LacdiNAc [β-GalpNAc(1→4)-β-GlcpNAc] element,
- Nitz, Mark,Bundle, David R.
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p. 3064 - 3073
(2007/10/03)
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- Synthesis of spacer-containing di- and tri-saccharides that represent parts of the capsular polysaccharide of Streptococcus pneumoniae type 6B
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In the framework of studies towards oligosaccharide-conjugate-based vaccines against Streptococcus pneumoniae, the synthesis is reported of several spacer-containing oligosaccharides that represent parts of the capsular polysaccharide of S. pneumoniae ser
- Thijssen, Mark J. L.,Van Rijswijk, Merlijn N.,Kamerling, Johannis P.,Vliegenthart, Johannes F. G.
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- Preparation of spacer-containing di-, tri-, and tetrasaccharide fragments of the circulating anodic antigen of Schistosoma mansoni for diagnostic purposes
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The chemical synthesis of β-D-GlcpA-(1→3)-β-D-GalpNAc-(1→O)CH2CH=CH2, β-D-GalpNAc-(1→6)-[β-D-GlcpA-(1→3)]-β-D-GalpNAc-(1→O)CH2CH =CH2, and β-D-GlcpA-(1→3)-β-D-GalpNAc-(1→6)-[β-D-GlcpA- (1→3)]-β-D-GalpNAc-(1→O)CH
- Halkes, Koen M.,Vermeer, Henricus J.,Slaghek, Ted M.,Van Hooft, Peter A. V.,Loof, Arnoud,Kamerling, Johannis P.,Vliegenthart, Johannes F. G.
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p. 175 - 188
(2007/10/03)
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- Synthesis of double-chain bis-sulfone neoglycolipids of the 2-, 3-, and 6-deoxyglobotrioses
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Partially protected 2-(trimethylsilyl)ethyl 2- and 3-deoxyglucosides and 6-deoxylactoside were synthesised via various routes and glycosylated with galabiosyl and galactosyl donors to give the corresponding deoxytrisaccharides. Removal of the protecting g
- Zhang, Zhiyuan,Magnusson, Goeran
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p. 2383 - 2393
(2007/10/03)
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- Conversion of p-methoxyphenyl glycosides into the corresponding glycosyl chlorides and bromides, and into thiophenyl glycosides
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p-Methoxyphenyl (pMP) β-D-glycopyranosides (Glc, Gal, GlcNPhth, GalNPhth, GlcNTroc, Galβ4Glc, Galα4Gal) were prepared from the corresponding 1-O-acetyl sugars in 79-90% yield, using boron trifluoride etherate as promoter. Treatment of the pMP glycosides with acyl chlorides or bromides in the presence of various Lewis acids gave the corresponding glycosyl chlorides and bromides in 81-98% yield. Treatment of the acyl-protected pMP glycosides with thiophenol and boron trifluoride etherate gave the corresponding thioglycosides in 80-100% yield and high (> 20:1) β/α selectivity. The stability of pMP glycosides was investigated against a series of reagents.
- Zhang, Zhiyuan,Magnusson, Goeran
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- Synthesis of hyaluronic acid-related di-, tri-, and tetra-saccharides having an N-acetylglucosamine residue at the reducing end
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The synthesis is reported of 4-methoxyphenyl O-(β-D-glucopyranosyluronic acid)-(1 → 3)-2-acetamido-2-deoxy β-D-glucopyranoside (1), 4-methoxyphenyl O-(2-acetamido-2-deoxy-β-D-glucopyranosyl)-(1 → 4)-O-(β-D-glucopyranosyluronic acid)-(1 → 3)-2-acetamido-2-
- Slaghek,Nakahara,Ogawa,Kamerling,Vliegenthart
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- Stereoselective total synthesis of the glycosyl phosphatidylinositol (GPI) anchor of Trypanosoma brucei
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The total synthesis of O--(1->2)-O-α-D-mannopyranosyl-(1->6)-O-6)-α-D-galactopyranosyl-(1->3)>-O-α-D-mannopyranosyl-(1->4)-2-amino-2-deoxy-α-D-glucopyranosyl>-(1->6)-1-O-(1,2-
- Murakata, Chikara,Ogawa, Tomoya
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- SYNTHESIS OF A SULFATED GLYCOPEPTIDE CORRESPONDING TO THE CARBOHYDRATE-PROTEIN LINKAGE REGION OF PROTEOGLYCANS: β-D-GlcA-(1->3)4)>-β-D-Gal-(1->3)-β-D-Gal-(1->4)-β-D-Xyl-(1->3)-Ser
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A sulfated glycotetraosyl serin 4 was synthesized in a stereocontrolled manner by employing a key glycotetraosyl donor 7 and a serine derivative 6.
- Goto, Fumitaka,Ogawa, Tomoya
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p. 5099 - 5102
(2007/10/02)
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