- Stereoselective O-Glycosylations by Pyrylium Salt Organocatalysis**
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Despite many years of invention, the field of carbohydrate chemistry remains rather inaccessible to non-specialists, which limits the scientific impact and reach of the discoveries made in the field. Aiming to increase the availability of stereoselective
- Holmstr?m, Thomas,Nielsen, Michael Martin,Pedersen, Christian Marcus
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supporting information
(2021/12/30)
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- Synthesis of nature product kinsenoside analogues with anti-inflammatory activity
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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)
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- A "traceless" Directing Group Enables Catalytic SN2 Glycosylation toward 1,2- cis-Glycopyranosides
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Generally applicable and stereoselective formation of 1,2-cis-glycopyranosidic linkage remains a long sought after yet unmet goal in carbohydrate chemistry. This work advances a strategy to this challenge via stereoinversion at the anomeric position of 1,2-trans glycosyl ester donors. This SN2 glycosylation is enabled under gold catalysis by an oxazole-based directing group optimally tethered to a leaving group and achieved under mild catalytic conditions, in mostly excellent yields, and with good to outstanding selectivities. The strategy is also applied to the synthesis of oligosaccharides.
- Fu, Yue,Liu, Peng,Ma, Xu,Zhang, Liming,Zheng, Zhitong,Zhu, Xijun
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supporting information
p. 11908 - 11913
(2021/08/20)
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- Visible-Light-Mediated β-C(sp3)-H Amination of Glycosylimidates: En Route to Oxazoline-Fused/Spiro Nonclassical Bicyclic Sugars
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A straightforward route has been developed for the diastereoselective synthesis of nonclassical conformationally constrained oxazoline-fused and spiro bicyclic sugars bearing a quaternary center via selective β-C-H amination of appropriately positioned gl
- Shaw, Mukta,Kumar, Amit
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supporting information
(2019/05/08)
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- An Empirical Understanding of the Glycosylation Reaction
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Reliable glycosylation reactions that allow for the stereo- and regioselective installation of glycosidic linkages are paramount to the chemical synthesis of glycan chains. The stereoselectivity of glycosylations is exceedingly difficult to control due to the reaction's high degree of sensitivity and its shifting, simultaneous mechanistic pathways that are controlled by variables of unknown degree of influence, dominance, or interdependency. An automated platform was devised to quickly, reproducibly, and systematically screen glycosylations and thereby address this fundamental problem. Thirteen variables were investigated in as isolated a manner as possible, to identify and quantify inherent preferences of electrophilic glycosylating agents (glycosyl donors) and nucleophiles (glycosyl acceptors). Ways to enhance, suppress, or even override these preferences using judicious environmental conditions were discovered. Glycosylations involving two specific partners can be tuned to produce either 11:1 selectivity of one stereoisomer or 9:1 of the other by merely changing the reaction conditions.
- Chatterjee, Sourav,Moon, Sooyeon,Hentschel, Felix,Gilmore, Kerry,Seeberger, Peter H.
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supporting information
p. 11942 - 11953
(2018/09/27)
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- Carbohydrate-lipid constructs and their use in preventing or treating viral infection
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The invention relates to selected carbohydrate-lipid constructs and their use as mimics of ligands for receptors expressed by virus. In particular, the invention relates to the use of selected carbohydrate-lipid constructs in methods of inhibiting virus infection and/or promoting clearance of virus from infected subjects. Carbohydrate-lipid constructs selected for use in these methods where the virus is Human Immunodeficiency Virus (HIV) are provided.
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Page/Page column 26
(2016/01/30)
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- Comparative Analysis of Fluorine-Directed Glycosylation Selectivity: Interrogating C2 [OH → F] Substitution in d- Glucose and d- Galactose
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The influence of C2 [OH → F] substitution on the stereochemical course of chemical glycosylation was interrogated in both D-glucose and its C4 epimer D-galactose. Molecular editing at C2 and configurational inversion at C4 were simultaneously investigated
- Santschi, Nico,Gilmour, Ryan
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supporting information
p. 6983 - 6987
(2015/11/16)
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- Efficient α-mannosylation of phenols: The role of carbamates as scavengers for activated glycosyl donors
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The boron trifluoride activation of trichloroacetimidate donors was found to be an efficient method for the α-mannosylation of tyrosine-containing acceptors. Most notably, these conditions are compatible with the commonly used carbamate protecting groups, whereas trichloroacetimidate activation with trimethylsilyl triflate or the use of glycosyl sulfoxides led to diminished yields in the presence of carbamates. In these cases, the competing reaction of the activated donors with the carbamate group was identified as a problematic side reaction. Taking advantage of this reactivity, various glycosyl carbamates were generated for the first time under non-acidic glycosylation conditions by reaction of different Boc-protected amino acids and dipeptides with glycosyl sulfoxides under triflic anhydride activation. Georg Thieme Verlag Stuttgart · New York.
- Schüler, Peter,Fischer, Sebastiann.,Marsch, Michael,Oberthür, Markus
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- Fluorine-directed β-galactosylation: Chemical glycosylation development by molecular editing
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Validation of the 2-fluoro substituent as an inert steering group to control chemical glycosylation is presented. A molecular editing study has revealed that the exceptional levels of diastereocontrol in glycosylation processes by using 2-fluoro-3,4,6-tri-O-benzyl glucopyranosyl trichloroacetimidate (TCA) scaffolds are a consequence of the 2R,3S,4S stereotriad. This study has also revealed that epimerization at C4, results in a substantial enhancement in β-selectivity (up to β/α 300:1). Copyright
- Durantie, Estelle,Bucher, Christoph,Gilmour, Ryan
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supporting information; experimental part
p. 8208 - 8215
(2012/08/27)
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- Monosaccharidic mimetics of the sialyl LewisX tetrasaccharide based on 2,7-dihydroxynaphthalene
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A potential monosaccharidic mimetic of the sialyl LewisX tetrasaccharide (sLeX) was identified based on an in silico docking study using the crystal structure of an E-selectin-sLeX complex. The chemical synthesis of the mimetic in an ortho-selective C-glycosylation is described. This compound and two close analogues were evaluated in a cell-based selectin binding assay where none of the tested mimetics showed an IC 50 below 1mM. This result can be explained by an unexpected 1C4 conformation of the mannosyl residue which precludes the required binding of the Ca2+-ion in E-selectin.
- Weck, Stefan,Frank, Martin,Hamann, Alf,Opatz, Till
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p. 134 - 148
(2013/09/24)
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- β-selective C-mannosylation of electron-rich phenols
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The reaction of tetra-O-benzylmannosyl trichloroacetimidate with electron-rich phenols in the presence of TMSOTf surprisingly leads to the exclusive formation of aryl β-C-glycosides while a preference for the -anomer could be observed with other Lewis aci
- Weck, Stefan,Opatz, Till
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supporting information; experimental part
p. 2393 - 2398
(2010/09/06)
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- Glycosylation catalyzed by a chiral bronsted acid
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"Chemical equation presented" The use of a chiral Bronsted acid catalyst for the activation of trichloroacetimidate glycosyl donors has been demonstrated for the first time. In toluene the chirality of the acid catalyst is seen to influence the stereochem
- Cox, Daniel J.,Smith, Martin D.,Fairbanks, Antony J.
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supporting information; experimental part
p. 1452 - 1455
(2010/06/20)
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- Total synthesis of the fully lipidated glycosylphosphatidylinositol (GPI) anchor of malarial parasite Plasmodium falciparum
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We report a new and convergent strategy for the total synthesis of fully lipidated glycosylphosphatidylinositol (GPI) anchor, the major pro-inflammatory factor of malarial parasite (Plasmodium falciparum). The key features of our approach include, the acc
- Ali, Asif,Vishwakarma, Ram A.
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scheme or table
p. 4357 - 4369
(2010/07/06)
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- CARBOHYDRATE-LIPID CONSTRUCTS AND THEIR USE IN PREVENTING OR TREATING VIRAL INFECTION
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The invention relates to selected carbohydrate-lipid constructs and their use as mimics of ligands for receptors expressed by virus. In particular, the invention relates to the use of selected carbohydrate-lipid constructs in methods of inhibiting virus infection and/or promoting clearance of virus from infected subjects. Carbohydrate-lipid constructs selected for use in these methods where the virus is Human Immunodeficiency Virus (HIV) are provided.
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- Some aspects of selectivity in the reaction of glycosyl donors
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Some advantages, disadvantages, and anomalies of various donors in glycosidations are discussed. By studying several two-component donor/acceptor-diol reactions, it is shown that regiopreferences are not very sensitive to the type of donor used. However,
- Uriel, Clara,Gomez, Ana M.,Lopez, J. Cristobal,Fraser-Reid, Bert
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p. 665 - 675
(2007/10/03)
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- A new approach to construct full-length glycosylphosphatidylinositols of parasitic protozoa and [4-deoxy-Man-III]-GPI analogues
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A new [2 + 2 + 2] approach to construct GPI molecules through the efficient synthesis of glucosamine-inositol and tetramannose intermediates led to a total synthesis of a GPI-anchor of Trypanosoma cruzi, and also afforded a key intermediate for the synthe
- Ali, Asif,Gowda, D. Channe,Vishwakarma, Ram A.
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p. 519 - 521
(2008/09/18)
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- SYNTHETIC MOLECULES HAVING IMMUNE ACTIVITY
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The present invention is directed to synthetic molecules having biological activity similar to PIM (acyl glycerol phosphatidylinositol manno-oligosaccharide) activity, for use in the treatment and prevention of inflammatory or immune cell mediated diseases or disorders.
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Page/Page column 36; 48
(2010/02/12)
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- Practical synthesis of KRN7000 from phytosphingosine
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The efficient and practical synthesis of die biologically important a-galactosylceramides, KRN7000, from phytosphingosine has been achieved in six steps in high overall yield.
- Kim, Sanghee,Song, Soyoung,Lee, Taeho,Jung, Sungkyu,Kim, Deukjoon
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p. 847 - 850
(2007/10/03)
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- Efficient chemical syntheses of branched cyclomalto-oligosaccharides using the trichloroacetimidate method
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Glycosylation using the trichloroacetimidate method was investigated in order to synthesize branched cyclomalto-oligosaccharides (cyclodextrins, CDs). We examined the chemical syntheses of galactosyl CDs, directly β-linked to the CD ring, which could not
- Ikuta, Akiko,Tanimoto, Toshiko,Koizumi, Kyoko
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p. 297 - 308
(2007/10/03)
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- A novel synthesis of α-D-Galp-(1→3)-β-D-Galp-1-Ο-(CH2) 3-NH2, its linkage to activated matrices and absorption of anti-αGal xenoantibodies by affinity columns
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Pig organs transplanted into primates are rapidly rejected because of the interaction between Galα(1→3)Gal epitopes carried by the graft and natural antibodies (anti-αGal antibodies) present in the blood of the recipient. This report describes a simplified synthesis of the xenogeneic disaccharide and its linkage to activated gel matrices. The digalactosides α-D-Galp-(1→3)-α,β-D-Galp-Galp were synthesized by the condensation of the trichloroacetimidoyl 2,3,4,6-tetra-Ο-benzyl-β-D-galactopyranoside donor with the 3,4-unprotected allyl 2,6-di-Ο-benzyl-α- or β-D-galactopyranoside acceptor precursor. Deallylation and hydrogenolysis led to the free digalactoside, whereas hydrogenolysis alone resulted in the 1-Ο-propyl digalactoside. Both products were tested by inhibition ELISA of natural anti-Gala(1→3)Gal antibodies. The α-D-Galp-(1→3)-β-D-Galp-OPr was found to be the best inhibitor. Thus, the allyl group of the partially benzylated α-D-Galp-(1→3)-β-D-Galp-OAll was engineered, via the hydroxy-, the tosyloxy- and the azidopropyl intermediates, into an aminopropyl group amenable to binding to N-hydroxysuccinimide-activated agarose gel matrices in order to obtain specific immunoabsorption columns. Columns made of gel substituted with 5 μmol of disaccharide per milliliter were found efficient for the immunoabsorption of anti-αGal antibodies from human plasma.
- Liaigre, Jér?me,Dubreuil, Didier,Pradère, Jean-Paul,Bouhours, Jean-Fran?ois
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p. 265 - 277
(2007/10/03)
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- Design and use of an oxazolidine silyl enol ether as a new homoalanine carbanion equivalent for the synthesis of carbon-linked isosteres of O- glycosyl serine and N-glycosyl asparagine
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A trimethylsilyl enol ether carrying the N-Boc 2,2-dimethyloxazolidine ring was designed to serve as a synthetic equivalent of the homoalanine carbanion for the introduction of the α-amino acid side chain at the anomeric carbon of sugars. This new functio
- Dondoni, Alessandro,Marra, Alberto,Massi, Alessandro
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p. 933 - 944
(2007/10/03)
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- A general approach to 1,2-trans-C-glycosides via glycosyl samarium(III) compounds
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The samarium diiodide reduction of glycosyl pyridyl sulfones with ketones or aldehydes under Barbier conditions leads to the instantaneous and stereospecific formation of 1,2trans-C-glycosides in good to acceptable yields. Mannosyl pyridyl sulfones 5ac,h
- Skrydstrup, Troels,Jarreton, Olivier,Mazéas, Daniel,Urban, Dominique,Beau, Jean-Marie
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p. 655 - 671
(2007/10/03)
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- Synthesis of a tetra-and a hexasaccharide donor corresponding to the non-reducing termini of mycobacterial 3-O-methylmannose polysaccharide (MMP)
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The blockwise synthesis of the title compounds, namely the tetra-and the hexasaccharide trichloroacetimidates (20) and (23), is described. Both acetates and imidates were employed as glycosyl donors in most of the coupling reactions. As nearly all of the
- Liao, Wensheng,Lu, Depei,Li, Aihong,Kong, Fanzuo
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p. 877 - 890
(2007/10/03)
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- Cardiac Glycosides. 7. Sugar Stereochemistry and Cardiac Glycoside Activity
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Digitoxigenin α-L, β-L, α-D, and β-D-glucosides; α-L-, β-L-, α-D-, and β-D-mannosides; and α-L- and β-L-rhamnosides were stereoselectively synthetized from the corresponding sugar tetrabenzyl trichloroacetimidates.The Na+, K+-ATPase receptor inhibitory activities of these glycosides (as a measure of receptor binding) were compared with those digitoxigenin, digitoxigenin 6'-hydroxy-β-D-digitoxide, digitoxigenin β-D-galactoside, and digitoxigenin β-D-digitoxoside.The observed activities reveal that a given sugar substituent may have a role in bindingof some glycoside stereoisomers, but not others.With α-L- and possibly β-L-rhamnosides, the 5'-CH3 and 4'-OH appear to have a predominant role in binding to the N+, K+-ATPase receptor.Addition of a 6'-OH to form the corresponding mannosides dramatically disrupts the effect of both the 5'-CH3 and 4'-OH in prompting receptor binding of the α-L isomer.However, with the β-L isomer, some influence of 4'-OH, 3'-OH, and 2'-OH binding remains.With β-D-glycosides, binding via the "5'-CH3 site" appears to be of little importance and addition of a 6'-OH diminishes activity only slightly.With these β-D-glycosides, and equatorial 4'-OH, axial 3'-OH, and equatorial 2'-OH groups appear to contribute to binding.
- Rathore, Hargovind,From, Arthur H. L.,Ahmed, Khalil,Fullerton, Dwight S.
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p. 1945 - 1952
(2007/10/02)
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- Glycosyl Imidates, 12. - Direct Synthesis of O-α- and O-β-Glycosyl Imidates
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1-O-Unsubstituted aldoses afford with halogen-activated nitriles under base catalysis directly O-α- and O-β-glycosyl imidates which can be isolated as stable compounds.Investigations with 2,3,4,6-tetra-O-benzyl- and -acetylglucose (1a, b), trichloroacetonitrile and trifluoroacetonitrile and NaH and K2CO3, respectively, as base have demonstrated, that the β-glucopyranosyl-1-oxido oxygen atom is more nucleophilic (rapid formation of 3a-β, 3b-β, 4a-β, and 4b-β) than the α-glycopyranosyl-1-oxido oxygen atom.Because of the reversibility of these reactions, however,due to the anomeric effect finally the thermodynamically more stable α-imidates 3a-α, 3b-α, 4a-α, and 4b-α are formed exclusively.Therefore O-α- and O-β-glycosyl imidate formation can be conducted highly diastereoselectively. - From trichloroacetonitrile and other 1-O-unsubstituted carbohydrates the imidates 7-α - 13-β were obtained as stable compounds. - Less activated nitriles (chloroacetonitrile, dichloroacetonitrile) have proven not or not so successful in the direct O-glycosyl imidate formation. - N-Aryl ketenimines yielded cleanly base-catalyzed direct O-glycosyl imidate formation.However, because of the irreversibility of this reaction under the reaction conditions only kinetic product formation was observed (leading to the β-imidates 14a-β - 14d-β and 15d-β.Similarly 1-O-unprotected mannose gave only the β-product 16d-β.
- Schmidt, Richard R.,Michel, Josef,Roos, Michael
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p. 1343 - 1357
(2007/10/02)
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