10343-06-3Relevant articles and documents
Shibaev et al.
, (1976)
A new efficient method for catalytic hydrolysis of thioglycoside
Uchiro, Hiromi,Wakiyama, Yoshinari,Mukaiyama, Teruaki
, p. 567 - 568 (1998)
A new and efficient method for catalytic hydrolysis of thioglycosides was successfully developed. Various thioglycosides were smoothly hydrolyzed to afford the corresponding 1-hydroxy sugars in high yields. The hydrolysis of disaccharides was took place smoothly without accompanying no anomerization of existing glycosidic bond.
Microbial mannosidation of bioactive chlorogentisyl alcohol by the marine-derived fungus Chrysosporium synchronum
Yun, Keumja,Kondempudi, Chinni Mahesh,Choi, Hong Dae,Kang, Jung Sook,Son, Byeng Wha
, p. 499 - 501 (2011)
The biological transformation of the biologically active chlorogentisyl alcohol (1), isolated from the marinederived fungus Aspergillus sp., was studied. Preparative-scale fermentation of chlorogentisyl alcohol with marine-derived fungus Chrysosporium synchronum resulted in the isolation of a new glycosidic metabolite, 1-O-(α-D-mannopyranosyl)chlorogentisyl alcohol (2). The stereostructure of the new metabolite obtained was assigned on the basis of detailed spectroscopic data analyses, chemical reaction, and chemical synthesis. Compounds 1 and 2 exhibited significant radical-scavenging activity against 1,1-diphenyl-2-picrylhydrazyl radical (DPPH) with IC50 values of 1.0 and 4.7 μM, respectively. The compounds 1 and 2 were more active than the positive control, L-ascorbic acid (IC50, 20.0 μM).
Regioselective hydrolysis of different peracetylated β-monosaccharides by immobilized lipases from different sources. Key role of the immobilization
Palomo, Jose M.,Filice, Marco,Fernandez-Lafuente, Roberto,Terreni, Marco,Guisan, Jose M.
, p. 1969 - 1976 (2007)
The effect of the immobilization strategy on the activity, specificity and regioselectivity of three different lipases [those from Thermomyces lanuginose (TLL), Aspergillus niger (ANL) and Candida antarctica B (CAL-B)] in the hydrolysis of peracetylated β-monosaccharides has been evaluated. Three very different immobilization strategies were utilized, covalent attachment, anionic exchange and interfacial activation on a hydrophobic support. The octyl-TLL immobilized preparation was the most efficient biocatalyst in the hydrolysis of 1,2,3,4,6-pentaO-acetyl-β-D-galactopyranose, producing specifically 6-hydroxy-l,2,3,4-tetra-O-acetyl-β-D-galactopyranose in 95 % overall yield, whereas the CNBr-TLL preparation was 48 times slower and regioselective towards the anomeric position, producing the 1-hydroxy derivative in 70% yield. The PEI-TLL immobilized preparation was the most efficient catalyzing the hydrolysis of 1,2,3,4,6-penta-O-acetyl-β-D-glucopyranose, permitting us to obtain up to 70% of the 6-hydroxy product. In the hydrolysis of 2-acetamido2-deoxy-l,3,4,6-tetra-0-acetyl-β-D-glucopyranose, the octyl-CALB preparation was not selective at all for the production of monohydroxy products whereas when CAL-B was immobilized on PEI-agarose, the enzyme was highly specific and regioselective producing the 6-hydroxy-2- acetamido-2-deoxy-l,3,4-tri-O-acetyl-β-D-glucopyranose in 70 % yield.
Synthesis of oligomeric mannosides and their structure-binding relationship with concanavalin A
Li, Chen-Wei,Hon, Kai-Wei,Ghosh, Bhaswati,Li, Po-Han,Lin, Hsien-Ya,Chan, Po-Han,Lin, Chun-Hung,Chen, Yu-Chie,Mong, Kwok-Kong Tony
, p. 1786 - 1796 (2014)
Small glycodendrimers with α-mannosyl ligands were synthesized by using copper-catalyzed azide-alkyne coupling chemistry and some of these molecules were used as multivalent ligands to study the induction of concanavalin A (Con A) precipitation. The results showed that the monovalent mannose ligand could induce the precipitation of Con A. This unexpected finding initiated a series of studies to characterize the molecular basis of the ligand-lectin interaction. The atypical precipitation is found to be specific to the mannose, fluorescein moiety (FITC), and Con A. Apparently the mannose ligand binds to Con A through hydrogen-bonding interactions, whereas the binding of FITC is mediated by hydrophobic forces. Being precipitate: A series of glycodendrimers with α-mannosyl ligands were prepared and used to explore the precipitation of concanavalin A (Con A). Surprisingly, the monovalent mannose ligand induced Con A precipitation, which led to an investigation of the molecular basis of the ligand-lectin interaction (see figure).
A solid phase reagent for the capture phosphorylation of carbohydrates and nucleosides.
Parang,Fournier,Hindsgaul
, p. 307 - 309 (2001)
[figure: see text] A 1% cross-linked divinylbenzene-polystyrene copolymer, containing cyanoethoxy N,N-diisopropylamine phosphine was prepared as a phosphitylating agent. The polymer-bound phosphitylated precursor was subjected to reaction with alcohols in the presence of 1H-tetrazole to produce the corresponding polymer-bound phosphite triesters. These were then oxidized with tert-butyl hydroperoxide to give the polymer-bound monophosphate triesters. Removal of cyanoethoxy on the resin with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) followed by basic cleavage of the p-hydroxybenzyl linker products yielded monophosphate derivatives.
Structurally diverse disaccharide analogs of antifreeze glycoproteins and their ability to inhibit ice recrystallization
Balcerzak, Anna K.,Ferreira, Sandra S.,Trant, John F.,Ben, Robert N.
, p. 1719 - 1721 (2012)
The β-D-galactosyl-(1,3)-α-N-acetyl-D-galactosamine disaccharide is present in antifreeze glycoproteins (AFGPs). Analogs of this disaccharide including the β-linked (1,3)-, (1,4)-, and (1,6)-galactosyl-N-acetyl galactosamine and the β-(1,3)-galactosyl-galactoside were synthesized and evaluated for ice recrystallization inhibition (IRI) activity. The results from this study demonstrate that the b-linked-(1,4) disaccharide exhibits more potent IRI activity than the native b-linked-(1,3) disaccharide. The C2 N-acetyl group of the disaccharide does not affect IRI activity but in monosaccharides, the presence of the C2 N-acetyl group decreases IRI activity. The current study will facilitate the design of potent small-molecule ice recrystallization inhibitors.
SYNTHESIS OF OLIGOSACCHARIDES BY USING LEVULINIC ESTER AS AN HYDROXYL PROTECTING GROUP
Koeners, H. J.,Verhoeven, J.,Boom, J. H.
, p. 381 - 382 (1980)
The fast, selective and mild removal of levulinyl groups with hydrazine from galactose, wich also carries hydroxyl functions protected with acetyl groups, enables, under Koenigs-Knorr conditions, the synthesis of a trimer containing β-linked galactoses.
Chemoenzymatic synthesis of a glycolipid library and elucidation of the antigenic epitope for construction of a vaccine against lyme disease
Stuebs, Gunthard,Rupp, Bernd,Schumann, Ralf R.,Schroeder, Nicolas W. J.,Rademann, Joerg
, p. 3536 - 3544 (2010)
Lyme disease (LD) is the most common tick-borne disease in Europe, North America, and Asia. The etiologic agents of LD are spirochetes of the group Borrelia burgdorferi sensu lato, which possess a lipid content of 25-30% of the dry weight. The major glycolipid cholesteryl 6-O-acyl-ss-D- galactopyranoside (ACGal), present in B. burgdorferi sensu stricto, B. afzelii, and B. garinii, is a specific and highly prevalent antigen frequently recognized by antibodies in late-stage LD. Here we report a convenient route for the chemical synthesis of ACGal by employing a combination of chemical synthesis steps with enzymatic transformations. This synthesized molecule was compared with bacterial extracts by immunoblots with patient sera, confirming the preserved antigenicity. Next, a glycolipid library derived from the native molecules with variations in the fatty acyl moiety and derivatives in which the cholesterol has been replaced was designed and synthesized. The chemical structures were confirmed by lD and 2D NMR spectroscopy and mass spectrometry. The native and synthetic glycolipids were utilized in immunoblots to determine the epitope recognized by antibodies in patient sera. By this method we could demonstrate that galactose, cholesterol, and a fatty acid with a minimal chain length of four carbon atoms comprises the essential structure for recognition by antibodies. Finally, this finding allowed the synthesis of a functionalized ACGal with an ω-mercapto group at the fatty acid and a facile protection and deprotection strategy. This antigenic hapten can be conjugated to a carrier protein to effect immunization against Lyme disease.
Regioselective anomeric deacetylation of peracetylated glycopyranoses
Bhaumik, Kankan,Salgaonkar, Paresh D.,Akamanchi
, p. 909 - 911 (2003)
A simple and mild method for regioselective anomeric deacetylation of peracetylated glycopyranoses using copper(II) acetate dihydrate and methanol/water (9:1) is described.
Esterase catalyzed regioselective hydrolyses of acetylated monosaccharides
Tomic, Srdanka,Ljevakovic, Durjica,Tomasic, Jelka
, p. 10977 - 10986 (1993)
Deacylations of fully acylated D-glucopyranoses, methyl D-glucopyranosides, 2-acetamido-2-deoxy-D-glucopyranoses glucopyranoses and methyl 2-acetamido-2-deoxy-D-glucopyranosides catalyzed by rabbit serum or the esterase isolated from rabbit serum were investigated. Depending on the structure of the acyl protecting group a high degree of regioselectivity is observed. Products of enzymic hydrolysis followed by intramolecular migrations of acetyl groups are also described.
Kawana,M.,Emoto,S.
, p. 3539 - 3546 (1969)
New glycosidase activated nitric oxide donors: Glycose and 3-morphorlinosydnonimine conjugates
Cai, T. Bill,Lu, Dongning,Tang, Xiaoping,Zhang, Yalong,Landerholm, Megan,Wang, Peng George
, p. 3518 - 3524 (2005)
(Chemical Equation Presented) To achieve site specific delivery of nitric oxide (NO), a new class of glycosidase activated NO donors has been developed. Glucose, galactose, and N-acetylneuraminic acid were covalently coupled to 3-morphorlinosydnonimine (SIN-1), a mesoionic heterocyclic NO donor, via a carbamate linkage at the anomeric position. The β-glycosides were successfully prepared for these conjugates, while the α-glycosidic compounds were very unstable. The new stable sugar-NO conjugates could release NO in the presence of glycosidases. Such NO prodrugs may be used as enzyme activated NO donors in biomedical research.
Synthesis of five-membered heterocycles by indirect electrochemical approach in Green media
Dures,Lombard,Pereira,Esteves,Medeiros
, p. G1 - G7 (2014)
Radical cyclization continues to be a central methodology for the preparation of natural products containing heterocyclic rings. Hence, some electrochemical results obtained by cyclic voltammetry and controlled-potential electrolysis in the study of electroreductive intramolecular cyclization of ethyl (2S, 3R)-2-bromo-3-propargyloxy-3-(2′,3′,4′,6′-tetra-O-acetyl-β-D-glucopyranosyloxy) propanoate (1a), 2-bromo-3-allyloxy-3-(2′,3′,4′,6′-tetra-O-acetyl-β-D-glucopyranosyloxy)propanoate (1b), 2-bromo-[1-(prop-2-yn-1-yloxy)propyl]benzene (1c) and [1-bromo-2-methoxy-2-(prop-2′-yn-1-yloxy)ethyl]benzene (1d) promoted by (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)nickel(I), [Ni(tmc)]+, electrogenerated at glassy carbon cathodes in ethanol and ethanol:water mixtures containing tetraalkylammonium salts, are presented. During controlled-potential electrolyses of solutions containing [Ni(tmc)]2+ and bromoalkoxylated compounds (1) catalytic reduction of the latter proceeds via one-electron cleavage of the carbon-bromine bond to form a radical intermediate that undergoes cyclization to afford the substituted tetrahydrofurans.
Regio- and stereo-selective bromo(alkoxylation)s of (E)-α-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxymethylene) carbonyl compounds. A route to near-stereopure α-bromo α-dioxymethyl carbonyl compounds
Idris, M. Sum,Larsen, David S.,Pritchard, Robin G.,Schofield, Anthony,Stoodley, Richard J.,Tiffin, Peter D.
, p. 2195 - 2204 (2000)
(E)-4-Methoxymethoxy-3-methylbut-3-en-2-one 17b reacts with NBS in propan-1-ol in a highly regio- and anti-stereo-selective manner to give (3R*-,4R*)-3-bromo-4-methoxymethoxy-3-methyl-4-propoxybutan-2-one 18. Compound 10, a relative of the butenone 17b in which the methoxymethyl group is replaced by the 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl unit, undergoes an analogous bromo(propoxylation) reaction with reasonable facial selectivity to give an 86:14 mixture of (3R,4R)-3-bromo-3-methyl-4-propoxy-4-(2′,3′,4′,6′-tetra- O-acetyl-β-D-glucopyranosyloxy)butan-2-one 11c and its (3S,4S)-diastereomer 12c. The major bromo(propoxy) derivative, isolable in 57% yield by fractional crystallisation, is assigned the stereostructure 11c by single-crystal X-ray crystallographic analysis. Other primary alcohols and methanol participate in the reaction of compound 10 with NBS, leading predominantly (with selectivities ranging from 75:25 to 89:11) to bromo(alkoxy) products of type 11 which are usually separable from their diastereomers of type 12 by fractional crystallisation (in yields ranging from 41 to 64%). A model to account for the role of the 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl unit in the stereoinduction process is proposed. Related bromo(propoxylation)s are observed with the vinylogous esters 24, 25a and 25b, leading to the isolation of the major products, 28, 30a and 30b (in yields ranging from 39 to 55%), and with the vinylogous carbonates 32a, 32c, 37a and 37b, providing access to the major products 33a, 33c, 38a and 38b (in yields ranging from 52 to 73%). In the presence of trifiuoroacetic acid and ethane-1,2-diol, the bromo(propoxy) derivatives 11c, 28, 30b and 33c undergo transacetalisation to give the ethylene glycol acetals 40a, 40b, 41 and 40c with ees of 94-98%, in yields ranging from 56 to 67%. The Royal Society of Chemistry 2000.
An alternative approach for the synthesis of sulfoquinovosyldiacylglycerol
Domey, Hendrik,Fischer, Judith,Rohn, Sascha,Sitz, Tobias
, (2021)
Sulfoquinovosyldiacylglycerol (SQDG) is a glycolipid ubiquitously found in photosyn-thetically active organisms. It has attracted much attention in recent years due to its biological ac-tivities. Similarly, the increasing demand for vegan and functional foods has led to a growing interest in micronutrients such as sulfolipids and their physiological influence on human health. To study this influence, reference materials are needed for developing new analytical methods and providing enough material for model studies on the biological activity. However, the availability of these materials is limited by the difficulty to isolate and purify sulfolipids from natural sources and the unavailability of chemical standards on the market. Consequently, an alternative synthetic route for the comprehensive preparation of sulfolipids was established. Here, the synthesis of a sulfolipid with two identical saturated fatty acids is described exemplarily. The method opens possibilities for the preparation of a diverse range of interesting derivatives with different saturated and unsatu-rated fatty acids.
Regioselective hydrolysis of peracetylated α-D-glucopyranose catalyzed by immobilized lipases in aqueous medium. A facile preparation of useful intermediates for oligosaccharide synthesis
Bastida, Agatha,Fernandez-Lafuente, Roberto,Fernandez-Lorente, Gloria,Guisan, Jose M.,Pagani, Giuseppe,Terreni, Marco
, p. 633 - 636 (1999)
Penta-O-acetyl-α-D-Glucopyranose was selectively deacetylated in aqueous media by lipases from Candida cilindracea (CCL) adsorbed on octyl- agarose support. Enzymatic hydrolyses was regioselective at the 4-position under neutral pH and towards the 6 position under acidic conditions. This enzymatic approach allows the one step synthesis of 1,2,3,6-tetra-O-acetyl- α-D-glucopyranoses 1, a useful intermediate in oligosaccharide synthesis.
cycloSaligenyl-mannose-1-monophosphates as a new strategy in CDG-Ia therapy: Hydrolysis, mechanistic insights and biological activity
Muus, Ulrike,Kranz, Christian,Marquardt, Thorsten,Meier, Chris
, p. 1228 - 1235 (2004)
Phosphomannomutase 2 (PMM-2) deficiency leads to an inefficient intracellular formation of mannose-1-phosphate (1), which causes an inherited metabolic disease with multisystemic abnormalities (Congenital Disorder of Glycosylation type Ia, CDG-Ia). In order to circumvent this metabolic deficiency, the cycloSal approach was applied for the intracellular delivery of mannose-1-monophosphate (1). cycloSaligenyl-pyranose-1-monophosphates 6-11 were obtained by a phosphitylation/oxidation procedure starting from appropriately protected D-pyranoses. The chemical hydrolysis data and the involved hydrolysis mechanisms of cyclosaligenyl-mannose-1-monophosphates 6-9 and their epimeric glucose analogues 10, 11 are reported. Furthermore, the biological activity of cycloSal-mannose-1-phosphates 6-9 was tested in vitro in PMM-2-deficient fibroblasts. 3-Methyl-cycloSal-2,3,4,6-tetra-O-acetyl-α-D-mannopyranose-1- monophosphate (8) showed a total correction of the phenotype, thus proving the delivery of mannose-1-phosphate. This may offer a suitable possibility for a therapy of CDG-Ia. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
Easy access to glycosyl phosphorothioates with microwaves technique
Cipolla, Laura,Redaelli, Cristina,Faria, Iris,Nicotra, Francesco
, p. 163 - 171 (2006)
A simple, efficient, and general method for the synthesis of glycosyl phosphorothioate through a one-pot reaction of glycosyl bromide with diethyl phosphite, ammonium acetate, and sulphur in the presence of alumina under solvent-free conditions using microwave irradiation has been developed. Copyright Taylor & Francis Group, LLC.
NIS/TFA: a general method for hydrolyzing thioglycosides
Dinkelaar, Jasper,Witte, Martin D.,van den Bos, Leendert J.,Overkleeft, Herman S.,van der Marel, Gijsbert A.
, p. 1723 - 1729 (2006)
A variety of thioglycosides are chemoselectively hydrolyzed to the corresponding 1-hydroxy glycosides using equimolar amounts of NIS/TFA as promoter systems.
Synthetic glycosides containing two isosteviol fragments functionalized with D-glucopyranose
Garifullin,Sharipova,Strobykina, I. Yu.,Babaev,Kataev
, p. 484 - 488 (2014)
The synthesis of isosteviol (16-oxo-ent-beyeran-19-oic acid) glycosides in which two isosteviol fragments functionalized with tetra-O-acetyl-D- glucopyranose are linked through a diester spacer is described for the first time.
Facile 1-O-deacylation of per-O-acylaldoses
Mikamo, Masatomo
, p. 150 - 153 (1989)
-
Synthesis of harounoside, a naturally occurring pentalongin hydroquinone bisglucoside
Van Nguyen, Tuyen,Claessens, Sven,Habonimana, Pascal,Tehrani, Kourosch Abbaspour,Van Puyvelde, Luc,De Kimpe, Norbert
, p. 2469 - 2471 (2006)
The recently isolated natural product harounoside, namely 5,10-dihydroxy-2H-naphtho[2,3-c]pyran-β-D-bisglucopyranoside, was conveniently synthesized for the first time from pentalongin in 84% yield over three steps. Georg Thieme Verlag Stuttgart.
Chemical synthesis of dolichyl phosphate and dolichyl glycosyl phosphates and pyrophosphates or "dolichol intermediates".
Warren,Jeanloz
, p. 122 - 137,124, 125 (1978)
-
BORON TRIFLUORIDE ETHERATE AS AN EFFECTIVE REAGENT FOR THE STEREOSELECTIVE ONE-POT CONVERSION OF ACETYLATED 2-TRIMETHYLSILYLETHYL GLYCOSIDES INTO SUGAR 1,2-TRANS-ACETATES.
Jansson, Karl,Frejd, Torbjoern,Kihlberg, Jan,Magnusson, Goeran
, p. 753 - 756 (1986)
Treatement of 2-trimethylsilylethyl glycosides with boron trifluoride etherate in the presence of acetic anhydride gave the corresponding sugar acetate in >90percent isolated yield and with a 1,2-trans:cis ratio of >20:1.The sugar with a free anomeric hydroxyl group was obtained when acetic anhydride was omitted.
Synthesis of malformin-A1, C, a glycan, and an aglycon analog: Potential scaffolds for targeted cancer therapy
Andreana, Peter R.,Hossain, Farzana,Nishat, Sharmeen
, (2022/02/21)
Improvement in therapeutic efficacy while reducing chemotherapeutic side effects remains a vital objective in synthetic design for cancer treatment. In keeping with the ethos of therapeutic development and inspired by the Warburg effect for augmenting biological activities of the malformin family of cyclic-peptide natural products, specifically anti-tumor activity, a β-glucoside of malformin C has been designed and synthesized utilizing precise glycosylation and solution phase peptide synthesis. We optimized several glycosylation procedures utilizing different donors and acceptors. The overarching goal of this study was to ensure a targeted delivery of a glyco-malformin C analog through the coupling of D-glucose moiety; selective transport via glucose transporters (GLUTs) into tumor cells, followed by hydrolysis in the tumor microenvironment releasing the active malformin C a glycon analog. Furthermore, total synthesis of malformin C was carried out with overall improved strategies avoiding unwanted side reactions thus increasing easier purification. We also report on an improved solid phase peptide synthesis protocol for malformin A1.
Rh2(II)-Catalyzed intermolecular N-Aryl aziridination of olefins using nonactivated N atom precursors
Deng, Tianning,Mazumdar, Wrickban,Yoshinaga, Yuki,Patel, Pooja B.,Malo, Dana,Malo, Tala,Wink, Donald J.,Driver, Tom G.
supporting information, p. 19149 - 19159 (2021/11/23)
The development of the first intermolecular Rh2(II)-catalyzed aziridination of olefins using anilines as nonactivated N atom precursors and an iodine(III) reagent as the stoichiometric oxidant is reported. This reaction requires the transfer of an N-aryl nitrene fragment from the iminoiodinane intermediate to a Rh2(II) carboxylate catalyst; in the absence of a catalyst only diaryldiazene formation was observed. This N-aryl aziridination is general and can be successfully realized by using as little as 1 equiv of the olefin. Di-, tri-, and tetrasubstituted cyclic or acylic olefins can be employed as substrates, and a range of aniline and heteroarylamine N atom precursors are tolerated. The Rh2(II)-catalyzed N atom transfer to the olefin is stereospecific as well as chemo- and diastereoselective to produce the N-aryl aziridine as the only amination product. Because the chemistry of nonactivated N-aryl aziridines is underexplored, the reactivity of N-aryl aziridines was explored toward a range of nucleophiles to stereoselectively access privileged 1,2-stereodiads unavailable from epoxides, and removal of the N-2,4-dinitrophenyl group was demonstrated to show that functionalized primary amines can be constructed.
First total syntheses of two natural glycosides
Dong, Hongbo,Du, Weihong,Yao, Zhongquan,Wu, Min,Luo, Hongbing,He, Yujiao,Cao, Shenghua
supporting information, (2020/12/02)
Isosyringinoside (1) and 3-(O-β-D-glucopyranosyl)-α-(O-β-D-glucopyranosyl)-4-hydroxy phenylethanol (2), the natural bioactive compounds contained unique structures, were first totally synthesized using easily available materials in short convenient routes with overall yields of 20.2% and 27.0%, respectively. An efficient total synthesis of 1 was developed in six steps, which contained two key steps of highly regioselective glycosylation without any selective protection steps. The seven-step synthesis of 2 involved two steps of regioselective glycosylations using BF3–O(C2H5)2 and TMSOTf as catalysts, respectively.
