cas 40591-65-9, 2-(2,3,4,6-TETRA-O-ACETYL-BETA-D-GLUCOPYRANOSYL)-2-THIOPSEUDOUREA HYDROBROMIDE

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Large-scale synthesis of thio-glucose-conjugated chlorin E6 for photodynamic therapy
Chlorin e6 is a heterocycle exhibiting spectral absorption in the 600-700 nm wavelength range used for photodynamic therapy (PDT). Herein, a sugar-conjugated chlorin e6 derivative was synthesized on a large scale. An alkyl spacer was fabricated by controlling the alkoxylation conditions between the thio-sugar and chlorin e6 and thio-glucose-conjugated chlorin e6 was successfully synthesized.
Hyakumura, Keisuke,Kataoka, Hiromi,Kodama, Shintaro,Masuda, Masato,Narumi, Atsushi,Nomoto, Akihiro,Ogawa, Akiya,Okamoto, Yoshiharu,Osaki, Tomohiro,Tanaka, Mamoru,Yamaguchi, Hiroaki,Yano, Shigenobu,Yoshimura, Tomokazu
(2021/06/21)

8-Hydroxyquinoline glycoconjugates containing sulfur at the sugar anomeric position—synthesis and preliminary evaluation of their cytotoxicity
One of the main factors limiting the effectiveness of many drugs is the difficulty of their delivery to their target site in the cell and achieving the desired therapeutic dose. Moreover, the accumulation of the drug in healthy tissue can lead to serious side effects. The way to improve the selectivity of a drug to the cancer cells seems to be its conjugation with a sugar molecule, which should facilitate its selective transport through GLUT transporters (glucose transporters), whose overexpression is seen in some types of cancer. This was the idea behind the synthesis of 8-hydroxyquinoline (8-HQ) derivative glycoconjugates, for which 1-thiosugar derivatives were used as sugar moiety donors. It was expected that the introduction of a sulfur atom instead of an oxygen atom into the anomeric position of the sugar would increase the stability of the obtained glycoconjugates against untimely hydrolytic cleavage. The anticancer activity of new compounds was determined based on the results of the MTT cytotoxicity tests. Because of the assumption that the activity of this type of compounds was based on metal ion chelation, the effect of the addition of copper ions on cell proliferation was tested for some of them. It turned out that cancer cells treated with glycoconjugates in the presence of Cu2+ had a much slower growth rate compared to cells treated with free glycoconjugates in the absence of copper. The highest cytotoxic activity of the compounds was observed against the MCF-7 cell line.
Erfurt, Karol,Hadasik, Agnieszka,Krawczyk, Monika,Pastuch-Gawo?ek, Gabriela
(2020/09/18)

POLYMER FOR DELIVERY OF BIOLOGICALLY ACTIVE MATERIALS
The present invention mainly relates to a polymer for delivery of biologically active materials, a complex and a method of synthesis thereof. The polymer comprises a poly(ethylene imine) and at least one monomer, each monomer comprising a modified sugar moiety, preferably galactose, comprising a sulphur atom or a nitrogen atom and a chemical moiety comprising a terminal epoxide for linking the polyethylene imine to the monomer, wherein the sulphur atom or the nitrogen atom links the modified sugar moiety to the chemical moiety. The biologically active material is preferably a gene, siRNA, mRNA, or plasmid DNA. Further disclosed is the medical use of said complex in treating a disease caused by a genetic disorder, for example cancer.
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(2019/01/17)

Combining Click Reactions for the One-Pot Synthesis of Modular Biomolecule Mimetics
Here, we report on the first combined one-pot use of the two so-called "click reactions": The thiol-ene coupling and the copper-catalyzed alkyne-azide cycloaddition. These reactions were employed in an alternating and one-pot fashion to combine appropriately functionalized monomeric carbohydrate building blocks to create mimics of trisaccharides and tetrasaccharides as single anomers, with only minimal purification necessary. The deprotected oligosaccharide mimics were found to bind both plant lectins and human galectin-3.
Brink?, Anne,Risinger, Christian,Lambert, Annie,Blixt, Ola,Grandjean, Cyrille,Jensen, Henrik H.
p. 7544 - 7548
(2019/10/08)

Improved Synthesis of Glucosinolates
Herein we describe an improved synthesis of glucosinolates, in which the quantity and cost of materials have been reduced by approximately an order of magnitude compared to typical literature procedures. This allowed us to produce multiple glucosinolates in 10-25 gram batches using vessel sizes no larger than 0.5 litres.
Lim, Yi Wee,Ong, Michelle Jui Hsien,Hewitt, Russell J.
p. 1640 - 1650
(2018/02/06)

A preparation method of the isothiourea hydrobromide
The invention relates to the sugar compound field, and concretely relates to a synthesis method of isothiourea dihydrobromide. The method comprises the following steps: adding acetic anhydride and a catalyst at room temperature, adding D-galactose, adding an acetic acid solution of hydrogen bromide after a reaction, adding the obtained reaction solution to thiourea and an acetonitrile solution with the temperature of 60-65DEG C in a dropwise manner, carrying out a temperature control reaction, post-processing to obtain 2-S-(2,3,4,6-tetra-O-acetyl-beta-D-galactopyranose)-2-isothiourea dihydrobromide with the purity of above 99%. The above compound is synthesized through the one-step reaction method, and the method has the advantages of simple operation, easily available raw materials, and operation cost and material saving.
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Paragraph 0026-0029; 0031-0034; 0036-0044; 0046-0048

(2018/11/03)

Electron-catalyzed radical perfluoroalkylation of organic sulfides: The serendipitous use of the TMEDA/I2 complex as a radical initiator
Radical initiation for the perfluoroalkylation reaction of sulfides has been performed using the complex [(TMEDA)I·I3] and visible light. This methodology bypasses the use of metal(organo)catalysts where the complex [(TMEDA)I·I3] acts as a good electron donor/reductant radical initiating agent. Biologically relevant sulfides are easily substituted with RF moieties employing a mild and environmentally benign radical strategy starting from readily available RFI.
Yerien,Barata-Vallejo,Camps,Cristófalo,Cano,Uhrig,Postigo
p. 2274 - 2282
(2017/07/24)

Stereoretentive palladium-catalyzed arylation, alkenylation, and alkynylation of 1-thiosugars and thiols using aminobiphenyl palladacycle precatalyst at room temperature
A general and efficient protocol for the palladium-catalyzed functionalization of mono- and polyglycosyl thiols by using the palladacycle precatalyst G3-XantPhos was developed. The C-S bond-forming reaction was achieved rapidly at room temperature with various functionalized (hetero)aryl-, alkenyl-, and alkynyl halides. The functional group tolerance on the electrophilic partner is typically high and anomer selectivities of thioglycosides are high in all cases studied. New sulfur nucleophiles such as thiophenols, alkythiols, and thioaminoacids (cysteine) were also successfully coupled to lead to the most general and practical method yet reported for the functionalization of thiols.
Bruneau, Alexandre,Roche, Maxime,Hamze, Abdallah,Brion, Jean-Daniel,Alami, Mouad,Messaoudi, Samir
p. 8375 - 8379
(2015/06/02)

Synthesis and characterization of novel cationic lipids derived from thio galactose
Two double chain cationic lipids QAS Cn -2-S (n = 12, 14) derived from thio galactose and carbamate-linkage tertiary amine were synthesized and their structures were confirmed by MS, TOF-MS, 1H NMR and 13C NMR. The QAS C12-2-S revealed superior surface activity compared with QAS C14-2-S with lower CMC and γCMC. Though Lipo C12-2-S displayed large average particle-size with high polydispersity, positive charged Lipo Cn -2-S can be combined with the negative charged DNA, also negatively stained TEM images confirmed the formation of vesicles. All the above prove that the Lipo Cn -2-S is helpful for gene transfection.
Qiao, Weihong,Zhou, Min,Luo, Limei
p. 261 - 268
(2014/03/21)

Preparation and X-ray analysis of potassium (2,3-dichlorophenyl) glucosinolate
There has been much interest in obtaining crystals for crystallographic analysis of biologically active glucosinolates. Crystals of potassium (2,3-dichlorophenyl)glucosinolate were obtained as a dual solvate, containing one methanol and one ethanol molecule of crystallization, K+ C 13H14Cl2NO9S2 - CH3OH C2H5OH. The three-dimensional polymeric network consists of chains containing the potassium ions coordinated and bridged by sugar O atoms, which run parallel to the a axis and are further crosslinked through the sugar molecules. The channels of this network are occupied by the dichlorophenyl substituents and the ethanol and methanol solvent molecules. The structure of the S-(2,3,4,6-tetra-O-acetyl- β-d-glucopyranosyl)-2,3-dichlorophenylacetothiohydroxymate, C 21H23Cl2NO10S, precursor has also been determined and the β-configuration and Z isomer of the thiohydroximate substituent is confirmed.
Vo, Quan V.,Trenerry, Craige,Rochfort, Simone,White, Jonathan,Hughes, Andrew B.
p. 588 - 594
(2014/08/18)

A concise chemical synthesis of a fluorescent βgal-(1,4)-S-βGlc- Cer derivative and its enzymatic elongation by glycosyltransferases
A straightforward chemical synthesis of lyso-lactosylceramide with the terminal galactose linked to glucose through a β-S-glycosidic bond is reported. The product is labeled on the amino-group with tetramethylrhodamine enabling its ultrasensitive detection in capillary electrophoresis using laser-induced fluorescence. The fluorescent product disaccharide is resistant to hydrolysis by glycosidases but is shown to remain as an acceptor substrate for glycosyltransferases for the conversion into the trisaccharides GM3 and Gb3.
Tanaka, Hidenori,Yoshimura, Yayoi,Dovichi, Norman J.,Palcic, Monica M.,Hindsgaul, Ole
supporting information; scheme or table
p. 1812 - 1815
(2012/05/04)

Efficient diverse approach for quinoxaline-derived glycosylated and morphinylated analogs
Sulfanyl-glycosides have been synthesized by reaction of 2,3-dimercaptoquinoxaline (1) with acetohalo sugars in presence of base to give the thioglycosides-derived quinoxalines 5-7 and 9. Similarly, the acyclic analogs 23-26 were prepared by coupling of 1 with different acyclo-alkylating agents. The preparation of 3-morpholinyl-quinoxalines 10 and 11 allowed the synthesis of 3-glycosylsulfanyl-2-morpholinyl-quinoxalines 12-14 and 17 as well as the acyclic analogs 27-29. Microwave irradiation of the reactants turned out to be preferred over the conventional method for achieving the synthetic goals. This study made an available venue to the synthesis of diverse quinoxaline derivatives.
Beldi, Razika,Atta, Kamal F.,Aboul-Ela, Sallah,El Ashry, El Sayed H.
body text
p. 50 - 56
(2011/04/16)

Surface glycosylation of polymer membrane by thiol-yne click chemistry for affinity adsorption of lectin
We present a novel approach to constructing glycosylated surface for microporous membrane. Carbohydrate derivative can be facilely bound onto the alkyne-modified membrane surface via thiol-yne click chemistry. The glycosylated membrane surface shows an excellent affinity adsorption to lectin on the basis of carbohydrate-protein recognition. The Royal Society of Chemistry.
Wang, Cang,Ren, Peng-Fei,Huang, Xiao-Jun,Wu, Jian,Xu, Zhi-Kang
supporting information; experimental part
p. 3930 - 3932
(2011/05/05)

Design and synthesis of bis-biotin-containing reagents for applications utilizing monoclonal antibody-based pretargeting systems with streptavidin mutants
Previous studies have shown that pretargeting protocols, using cancer-targeting fusion proteins, composed of 4 anti-CD20 single chain Fv (scFv) fragments and streptavidin (scFv4-SAv), followed by a biotinylated dendrimeric N-acetyl-galactosamine blood clearing agent (CA), 1, then a radiolabeled DOTA-biotin derivative (a monobiotin), 3a, can provide effective therapy for lymphoma xenografts in mouse models. A shortcoming in this pretargeting system is that endogenous biotin may affect its efficacy in patients. To circumvent this potential problem, we investigated a pretargeting system that employs anti-CD20 scFv4-SAv mutant fusion proteins with radioiodinated bis-biotin derivatives. With that combination of reagents, good localization of the radiolabel to lymphoma tumor xenografts was obtained in the presence of endogenous biotin. However, the blood clearance reagents employed in the studies were ineffective, resulting in abnormally high levels of radioactivity in other tissues. Thus, in the present investigation a bis-biotin-trigalactose blood clearance reagent, 2, was designed, synthesized, and evaluated in vivo. Additionally, another DOTA-biotin derivative (a bis-biotin), 4a, was designed and synthesized, such that radiometals (e.g., 111In, 90Y, 177Lu) could be used in the pretargeting protocols employing scFv4-SAv mutant fusion proteins. Studies in mice demonstrated that the CA 2 was more effective than CA 1 at removing [125I]scFv4-SAv-S45A mutant fusion proteins from blood. Another in vivo study compared tumor targeting and normal tissue concentrations of the new reagents (2 and [111In]4b) with standard reagents (1 and [111In]3b) used in pretargeting protocols. The study showed that lymphoma xenografts could be targeted in the presence of endogenous biotin when anti-CD20 fusion proteins containing SAv mutants (scFv 4-SAv-S45A or scFv4-SAv-Y43A) were employed in combination with CA 2 and [111In]4b. Importantly, normal tissue concentrations of [111In]4b were similar to those obtained using the standard reagents (1 and [111In]3b), except that the blood and liver concentrations were slightly higher with the new reagents. While the reasons for the higher blood and liver concentrations are unknown, the differences in the galactose structures of the clearance agents 1 and 2 may play a role.
Wilbur, D. Scott,Park, Steven I.,Chyan, Ming-Kuan,Wan, Feng,Hamlin, Donald K.,Shenoi, Jaideep,Lin, Yukang,Wilbur, Shani M.,Buchegger, Franz,Pantelias, Anastasia,Pagel, John M.,Press, Oliver W.
experimental part
p. 1225 - 1238
(2011/04/24)

One-pot synthesis of hyperbranched poly(amido amine) clicked with a sugar shell via Michael addition polymerization and thiol click reaction
This paper reports the production of glycopolymers via a simple and flexible method. A novel glycopolymer with a hyperbranched poly(amido amine) core and a sugar shell (HPAA-GLc) was synthesized by using thiol-ene click reaction via facile one-pot method. Hyperbranched poly(amido amine) with vinyl terminals was first synthesized by Michael addition polymerization of N,N′-methylene bisacrylamide (MBA) with 1-(2-aminoethyl) piperazine (AEPZ). Subsequently, thiol-ene click reaction between vinyl units of hyperbranched poly(amido amine) and thio-glucose was performed in situ. Based on the NMR result, all the vinyl groups reacted with thiol-glucose in 120 min. Strong photoluminescence emission was observed from the aqueous solution of HPAA-GLc. Science China Press and Springer-Verlag Berlin Heidelberg 2010.
Yu, Zhiqiang,Cui, Mengmeng,Yan, Junjie,You, Yezi
experimental part
p. 1663 - 1668
(2011/01/13)

Synthesis of novel thioglycoside derivatives containing quinazolinone
Aseries of novel thioglycoside derivatives containing 4(3H)-quinazolinone was designed and synthesized from 2-chloromethyl-quinazolin-4(3H)-ones and 1-thioglycose. Several 2-chloromethyl-quinazolin-4(3H)-ones were synthesized on refluxing with 2-(chloroacetylamino)-benzoic acid and arylamines in acetonitrile. All of the novel compounds were characterized by IR, 1H NMR spectra and elemental analysis. The structures of compounds 7b, 8b and 8c have been determined by X-ray diffraction analysis.
Huang, Hui,Gao, Jian-Fang,Cao, Ling-Hua,Wang, Duo-Zhi,Zhang, Jian-Bin,Zhou, Shu-Bao,Zhou, Yu-Qiang
scheme or table
p. 419 - 424
(2009/12/06)

Thiyl glycosylate of olefinic proteins: S-linked glycoconjugate synthesis
Tagged for thiolation: A novel glycoconjugation strategy utilizes a non-natural olefin-containing amino acid (homoallylglycine, Hag) as a "tag" for modification and a photoinitiated hydroglycothiolation reaction that is selective only for the Hag olefinic "tag". Application of this method to a number of model proteins allowed complete and precise site-selective glycosylate generating glycoconjugates that include, for example, virus-like particles displaying up to 180 glycans at preselected positions (see scheme).
Floyd, Nicola,Vijayakrishnan, Balakumar,Koeppe, Julia R.,Davis, Benjamin G.
supporting information; experimental part
p. 7798 - 7802
(2010/04/05)

Solvent-free synthesis of thioglycosides by ball milling
Thioglycosides have been prepared in excellent yields by three different routes from a range of readily available glycosyl halides under solvent-free conditions employing a planetary ball mill.
Ramrao Patil, Premanand,Ravindranathan Kartha
experimental part
p. 953 - 956
(2010/04/23)

Application of HOF·CH3CN to the synthesis of glycosyl sulfones
A fast, complete and clean conversion of thioglycosides into glycosyl sulfones under mild acidic conditions is described, using the HOF·CH3CN complex at room temperature. This methodology affords glycosyl sulfones in high yields and in excellent purity.
Morais, Goreti Ribeiro,Humphrey, Andrew J.,Falconer, Robert A.
p. 7426 - 7431
(2008/12/20)

Synthesis of positional thiol analogs of β-D-galactopyranose
Approaches toward the synthesis of thio-β-D-galactose derivatives are described. These compounds were prepared from the parent carbohydrates: D-galactose, methyl β-D-galactoside and methyl β-D-glucoside, respectively. It was found that not only the strategies of protecting group introduction and selective deprotection, but also the choices of solvent and nucleophilic reagent concentration were crucial to allow the efficient introduction of sulfur at different positions of the galactose ring. The effects from the solvent, the nucleophilic reagent concentration, and the protecting group patterns have been investigated. The results clearly show that ester protecting groups play highly important roles for the synthesis of thio-containing carbohydrates, requiring nonpolar solvents to suppress the neighboring group participation. For the Lattrell-Dax (nitrite-mediated) inversion reaction, employed in the synthetic route to the 2-thio-β-D- galactoside, intramolecular nucleophilic attack, as well as stronger stereospecific ester activation, are necessary to overcome hindrance from 4,6-O-benzylidene protection. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
Pei, Zhichao,Dong, Hai,Caraballo, Remi,Ramstroem, Olof
p. 4927 - 4934
(2008/03/14)

SYNTHESIS AND USE OF GLYCODENDRIMER REAGENTS
The present invention relates to a chemically modified mutant protein including a cysteine residue substituted for a residue other than cysteine n a precursor protein, the substituted cysteine residue being subsequently modified by reacting the cysteine residue with a glycosylated thiosulfonate. Also a method of producing the chemically modified mutant protein is provided. The present invention also relates to a glycosylated methanethiosulfonate. Another aspect of the present invention is a method of modifying the functional characteristics of a protein including providing a protein and reacting the protein with a glycosylated methanethiosulfonate reagent under conditions effective to produce a glycoprotein with altered functional characteristics as compared to the protein. In addition, the present invention relates to methods of determining the structure-function relationships of chemically modified mutant proteins. The present invention also relates to synthetic methods for producing thio-glycoses, the thio-glycoses so produced, and to methods for producing glycodendrimer reagents.
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Page/Page column 44; 54; sheet 19

(2010/11/08)

REAGENTS AND METHODS FOR THE FORMATION OF DISULFIDE BONDS AND THE GLYCOSYLATION OF PROTEINS
Methods and reagents for the formation of disulfide bonds, particularly in proteins, peptides and amino acids. The methods and reagents are particularly useful for the controlled glycosylation of proteins, peptides and amino acids. The methods utilise thiosulfonate or selenenylsulfide compounds as reagents or intermediates. Some proteins and peptides comprising selenenylsulfide groups also form part of the invention.
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Page/Page column 22

(2010/02/10)

Glycoviruses: Chemical glycosylation retargets adenoviral gene transfer
A sugar-specific transfection mechanism is introduced by the glycosylation of adenoviruses (AVs, see picture), and manipulation of the glycosylation pattern allows the selective transfection of human macrophages in favor of the usual target. This dramatic retargeting holds promise for the fine-tuning of adenoviruses for applications such as gene therapy.
Pearce, Oliver M. T.,Fisher, Kerry D.,Humphries, Julia,Seymour, Leonard W.,Smith, Alberto,Davis, Benjamin G.
p. 1057 - 1061
(2007/10/03)

Synthesis of interglycosidically S-linked 1-thio-oligosaccharides under microwave irradiation
Microwave irradiation (MWI) has accelerated the synthesis of S-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)thiouronium bromide (2a), whose reaction with 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide (1a) in the presence of Et3N afforded stereoselectively the acetylated β,β-1-thiotrehalose 4a. Similarly, the respective D-galactopyranosyl 4b and 2-acetylamino-2-deoxy-D-glucopyranosyl 4c analog as well as 4,4′-di-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl) 4d and 4,4′-di-O-(2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl) 4e derivatives of 2,2′,3,3′,6,6′-hexa-O-acetyl β,β-1-thiotrehalose were prepared. Copyright Taylor & Francis, Inc.
El Ashry, El Sayed H.,Awad, Laila F.,Hamid, H. M. Abdel,Atta, Atta I.
p. 745 - 753
(2007/10/03)

Glyco-SeS: Selenenylsulfide-mediated protein glycoconjugation - A new strategy in post-translational modification
Site-selective glycosylation by Se-S-mediated ligation has led to the efficient formation of a wide variety of conjugates 1 without the need for a large excess of the carbohydrate reagent. By this convergent method it was possible to introduce a heptasaccharide glycan selectively, and to perform a multiple site-selective chemical glycosylation of protein. A chemically Cysglycosylated glycoprotein was elaborated enzymatically.
Gamblin, David P.,Garnier, Philippe,Van Kasteren, Sander,Oldham, Neil J.,Fairbanks, Antony J.,Davis, Benjamin G.
p. 828 - 833
(2007/10/03)

A general procedure for conversion of S-glycosyl isothiourea derivatives into thioglycosides, thiooligosaccharides and glycosyl thioesters
A simple procedure for conversion of S-glycosyl isothiourea derivatives into thioglycosides by promotion with triethylamine is described. The reaction conditions allow the synthesis of glycosyl thioesters and some thioglycosides, which cannot be prepared using the traditional approach. The procedure has been successfully applied for preparation of thiooligosaccharides, shown by syntheses of methyl 4-thio-α-cellobioside and methyl 4-thio-α-lactoside derivatives.
Ibatullin,Selivanov,Shavva
p. 419 - 422
(2007/10/03)

Synthesis of spacer-armed glucodendrimers based on the modification of poly(propylene imine) dendrimers
The use of preformed poly(propylene imine) dendrimers [DAB(Pa)x] with reactive primary amine end groups proved to be very useful for the construction of saccharide surfacecoated dendrimers. For this purpose, amide bonds were introduced by a reaction between the primary amine end groups of the dendrimers with N-succinimidyl-activated esters of spacer-armed acetyl-protected thioglucopyranoside units. The linear alkyl chain spacers between the dendrimer surface and the saccharide units was increased in length with 1, 5 and 10 carbon atoms. These spacer arms were introduced to determine the influence of local saccharide surface concentration variations on the dendrimer properties. After modification of the dendrimers with these saccharide units, the acetyl protecting groups were removed. Purification of these derivatives was accomplished by using dialysis either in water or in aqueous methanol. The solubility behavior of the resulting glucodendrimers proved to be strongly dependent on the hydrophobic part, i.e. the alkyl chain spacers in the molecule. Therefore, these nanosized multivalent structures, appropriate for studying carbohydrate-protein interactions, are also proposed useful for investigating amphiphilic properties.
Peerlings,Nepogodiev, Sergey A.,Stoddart, J. Fraser,Meijer
p. 1879 - 1886
(2007/10/03)

Preparation and reactions of 2-chloroethyl 1-thio-β-D-glycopyranosides derived from D-galactose, D-glucose, and 2-acetamido-2-deoxy-D-glucose
Chloroethyl 1-thio-β-D-glycopyranosides of the D-galacto and D-gluco configurations 5a-5c were prepared by alkylation of the corresponding 1-thio-β-D-hexopyranoses 3a-3c with 1-bromo-2-chloroethane followed by deacetylation. The starting 1-thio-β-D-hexopyranoses were obtained from the acetylated glycopyranosyl halides via isothiouronium salts. It was demonstrated that the chloroethyl thioglycosides 5a-5c undergo hydrolysis in aqueous solutions to give the 2-hydroxyethyl thioglycosides 6a-6c and reducing hexoses and that this hydrolysis proceeds via episulfonium salts. The hydrolysis was monitored by 1H and 13C NMR spectroscopy. In 1% aqueous solutions of sodium carbonate containing phenol or aniline, the thioglycosides 5a-5c provide, in addition to the above hydrolysis products, also the phenoxyethyl and phenylaminoethyl thioglycosides 9a, 10a and 9b, 10b, respectively.
Cerny, Miloslav,Trnka, Tomas,Budesinsky, Milos
p. 1489 - 1500
(2007/10/03)

Facile synthesis of 1,2-trans-nitrophenyl-1-thioglycopyranosides
1,2-trans-2-Nitro-, 4-nitro- and 2,4-dinitrophenyl-1-thioglycopyranosides were synthesized in high yield by condensation of per-O-acetyl-1-thioglucose with the appropriate nitro- or dinitrofluorobenzene in the presence of potassium carbonate. The pseudothiourea precursor was also used under these coupling conditions. 1,2-trans-4-Nitrophenyl-1-thioglycosides derived from β-D-galactose, β-D-xylose, α-L-arabinose and maltose were also obtained in good yield.
Driguez,Szeja
p. 1413 - 1414
(2007/10/02)

LINOMYCIN ANALOGUES. II. CHAIN EXTENSION OF METHYL-6-ALDEHYDO-3,4-O-ISOPROPYLIDENE-1-THIO-β-D-GALACTO-1,5-PYRANOSIDE
Synthesis of methyl 2,3,4,6-tetra-O-acetyl-1-thio-α-D-galactopyranoside and its β-anomer (3 and 4) from the 2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl bromide via the isothiouronium salt in HMPT involved a considerable increase in the proportion of the α-anomer.Deacetylation of (3 and 4) with sodium methoxide yielded 5 and 6 respectively.Conversion of 6 into corresponding 3,4-isopropylidene derivative (7) followed by oxidation with Collin reagent gave the aldehydo-sugar (8) which when reacted with the stabilized phosphorane led in the excellent yield to the Z-unsaturated bromo-sugar (9).
Tronchet, Jean M. J.,Massoud, Mohamed A. M.
p. 1265 - 1269
(2007/10/02)

Synthesis of Alkyl-β-D-thioglucopyranosides, a Series of New Nonionic Detergents
As a part of our search for new types of detergent useful for biological applications, a series of alkyl-β-D-thioglucopyranosides was synthesized in several steps from glucose.The overall yield was about 80percent.Critical micelle concentrations of n-hexyl-, n-heptyl-, n-octyl-, and n-nonyl-β-D-thioglucopyranoside were determined.Because of their electroneutrality, high solubility in water and high critical micelle concentration, n-heptyl- and n-octyl-β-D-thioglucopyranoside seem to be potentially useful detergents for applications in biological systems.
Saito, Setsuo,Tsuchiya, Tomofusa
p. 503 - 508
(2007/10/02)

Synthesis of some N- and S-glycosides of D-galactose bearing hydrazinocarbonyl and diazomethylcarbonyl functions in the aglycon
We describe the synthesis of N- and S-glycosides derived from D-galactopyranose in which the aglycon bears certain reactive groups.In a first series, the anomeric carbon is linked to an amino group that is acylated by a functionalized succinic acid chain.The terminal group of the aglycon moiety is a hydrazide function which can be converted by ultraviolet light irradiation into an azide and a nitrene.Altenatively, the terminal group is a diazoketone function which can be converted into a carbene, by ultraviolet light irradiation.A second series comprises glycosides of 1-thio-β-D-galactopyranose.The aglycon consists of a 6-carbon chain with a carboxylic end group.The latter has been converted into a hydrazide and diazoketone function.We show that the diazo group of the diazoketones (compounds 5 and 12) is susceptible to decomposition by ultraviolet irradiation, being nearly quantitatively decomposed after 3 minutes.These compounds add to a growing list of hexose derivatives which can be used in the field of photoaffinity-labeling of the sugar binding sites of certain lectins and of hexose transport systems, or to prepare modified proteins or ligands for affinity chromatography.
Dupuis, Gilles,Leclair, Benoit
p. 2531 - 2536
(2007/10/02)

INSULIN-LIKE, AND INSULIN-ANTAGONISTIC, CARBOHYDRATE DERIVATIVES. THE SYNTHESIS OF ARYL AND ARALKYL D-MANNOPYRANOSIDES AND 1-THIO-D-MANNOPYRANOSIDES
A number of novel, aryl and aralkyl D-mannopyranosides and 1-thio-D-mannopyranosides were synthesized for evaluation of insulin-like and insulin-antagonistic properties.The substituted-phenyl α-D-mannopyranosides were prepared by the general procedure of Helferich and Schmitz-Hillebrecht, the substituted-phenyl 1-thio-α-D-mannopyranosides by a method corresponding to the Michael synthesis of aromatic glycosides, and the aralkyl 1-thio-α-D-mannopyranosides by aralkylation of 2,3,4,6-tetra-O-acetyl-1-thio-α-D-mannopyranose 15 and subsequent O-deacetylation.Compound (15) was obtained by basic cleavage of the amidino group in 2-S-(tetra)-O-acetyl-α-D-mannopyranosyl)-2-thiopseudourea hydrobromide, the product of the reaction of tetra-O-acetyl-α-D-mannosyl bromide with thiourea.Benzyl 1-thio-β-D-mannopyranoside, obtained by reaction of the sodium salt of 1-thio-β-D-mannopyranose with α-bromotoluene, and benzyl 1-thio-α-L-mannopyranoside were also synthesized, in order to asses the stereospecificity of the biological activites measured.
Durette, Philippe L.,Shen, Tsung Y.
p. 261 - 274
(2007/10/02)

Synthesis of glucosinolates
A high yielding synthesis of 2-phenethylglucosinolate is described. The method should also be directly applicable to most (if not all) other glucosinolates.
Gil,MacLeod
p. 779 - 783
(2007/10/02)