- Mapping the Relationship between Glycosyl Acceptor Reactivity and Glycosylation Stereoselectivity
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The reactivity of both coupling partners—the glycosyl donor and acceptor—is decisive for the outcome of a glycosylation reaction, in terms of both yield and stereoselectivity. Where the reactivity of glycosyl donors is well understood and can be controlled through manipulation of the functional/protecting-group pattern, the reactivity of glycosyl acceptor alcohols is poorly understood. We here present an operationally simple system to gauge glycosyl acceptor reactivity, which employs two conformationally locked donors with stereoselectivity that critically depends on the reactivity of the nucleophile. A wide array of acceptors was screened and their structure–reactivity/stereoselectivity relationships established. By systematically varying the protecting groups, the reactivity of glycosyl acceptors can be adjusted to attain stereoselective cis-glucosylations.
- van der Vorm, Stefan,van Hengst, Jacob M. A.,Bakker, Marloes,Overkleeft, Herman S.,van der Marel, Gijsbert A.,Codée, Jeroen D. C.
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supporting information
p. 8240 - 8244
(2018/05/03)
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- Synthesis and mass spectrometric analysis of disaccharides from methanolysis of heparan sulfate
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The quantification of heparan sulfate (HS) in biological matrices, e.g., urine, cerebrospinal fluid, tissue samples etc., is of great importance for the diagnosis and prognosis of several of the mucopolysaccharidosis (MPS) disorders, which are lysosomal storage diseases of impaired glycosaminoglycan metabolism. The development of suitable assays for this purpose is challenging due to the high molecular weight and complexity of HS. Recent efforts towards this goal include the acid catalysed methanolysis of HS, which desulfates the polymer and results in the formation of disaccharide cleavage products which can be detected and quantified by LC-MS/MS. We have synthesized a library of 12 HS-derived disaccharides as methanolysis standards via the stereoselective 1,2-cis glycosylation of suitably protected GlcA and IdoA acceptors with a 2-deoxy-2-azido thioglucoside donor. This facilitated identification of the major peaks in the LC-MS/MS chromatograms, and potentially will allow the monitoring of specific metabolites as surrogate markers for genotype. This work also paves the way towards a fully quantitative LC-MS/MS assay for HS via the preparation of a suitably labelled derivative.
- He, Qi Qi,Trim, Paul J.,Snel, Marten F.,Hopwood, John J.,Ferro, Vito
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p. 8791 - 8803
(2018/11/30)
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- A green and convenient method for regioselective mono and multiple benzoylation of diols and polyols
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An efficient method for regioselective benzoylation of diols and polyols was developed. The benzoylation is catalyzed by only 0.2 equiv of benzoate anion in acetonitrile with the addition of a stoichiometric amount of benzoic anhydride under very mild condition, leading to high yields. Compared with all other methods, this method shows particular advantage in regioselective multiple benzoylation of polyols, and in avoiding the use of any metal-based catalysts and any amine bases, which is more environment-friendly.
- Zhang, Xiaoling,Ren, Bo,Ge, Jiantao,Pei, Zhichao,Dong, Hai
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supporting information
p. 1005 - 1010
(2016/02/03)
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- Regioselective mono and multiple alkylation of diols and polyols catalyzed by organotin and its applications on the synthesis of value-added carbohydrate intermediates
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A catalytic amount of dibutyltin dichloride was used to develop regioselective alkylation of diols and multiple alkylation of polyols. Alkyl groups, including allyl, alkynyl and long-chain alkyl groups, were successfully introduced to one or two hydroxyl
- Xu, Hengfu,Ren, Bo,Zhao, Wei,Xin, Xiaoting,Lu, Yuchao,Pei, Yuxin,Dong, Hai,Pei, Zhichao
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p. 3490 - 3499
(2016/06/06)
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- Selective 4,6-O-benzylidene formation of methyl α-d-mannopyranoside using 2,6-dimethylbenzaldehyde
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While methyl α-d-glucopyranosides and α-d-galactopyranosides selectively form 4,6-O-benzylidenes when reacted with excess benzaldehyde in the presence of acid catalyst methyl α-d-mannopyranosides does not exhibit the same selectivity because of the cis-ar
- Liotta, Louis J.,Chalmers, Jennifer F.,Falco Marshall, Jessica N.,Ferreira, Timothy E.,Mullen, Hannah E.,Pace, Nicholas J.
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- Halide promoted organotin-mediated carbohydrate benzylation: Mechanism and application
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In the present study, the mechanistic origin of the promoted organotin-mediated carbohydrate benzylation by halides was explored by the comparison of the activation ability of halides on benzylation of methyl β-d-galactoside. It was demonstrated that the
- Zhou, Yixuan,Li, Jinyang,Zhan, Yingjie,Pei, Zhichao,Dong, Hai
-
supporting information
p. 2693 - 2700
(2013/03/28)
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- Enantioselective alkylation of aldehydes using dialkylzincs catalyzed by simple chiral diols derived from naturally occurring monosaccharides
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Enantioselective alkylation of aldehydes was achieved in up to 84% ee using dialkylzincs catalyzed by simple diols derived from naturally occurring monosaccharides.
- Michigami, Kyosuke,Hayashi, Masahiko
-
supporting information
p. 4221 - 4225
(2013/06/27)
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- Carbohydrate-derived PSE acetals: Controlled base-induced ring cleavage
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Retro-Michael type reactions applied to PSE acetals protecting monosaccharides led either to complete removal or to ring-cleavage. In protic medium, application of standard basic conditions resulted in acetal deprotection, while the use of butyl lithium in aprotic medium allowed controlled ring-cleavage. A regio- and stereoselective C- over O-alkylation was observed during the process. Furthermore, depending on the substrates and the reaction conditions involved, new carbohydrate-derived β-alkoxyvinyl sulfones were obtained with varying regioselectivity.
- Chéry, Florence,Cabianca, Elena,Tatibou?t, Arnaud,De Lucchi, Ottorino,Rollin, Patrick
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experimental part
p. 544 - 551
(2012/01/14)
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- Construction of triazolyl bidentate glycoligands (TBGs) by grafting of 3-azidocoumarin to epimeric pyranoglycosides via a fluorogenic dual click reaction
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Glycoligands, which feature a glycoside as the central template incorporating Lewis bases as metal chelation sites and various fluorophores as the chemical reporter, represent a range of interesting scaffolds for development of chemosensors. Here, new typ
- Xue, Jia-Lu,He, Xiao-Peng,Yang, Jin-Wei,Shi, De-Tai,Cheng, Chao-Ying,Xie, Juan,Chen, Guo-Rong,Chen, Kaixian
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- Synthesis of novel photolabile glycosides from methyl 4,6-O-(o-nitro)benzylidene-α-d-glycopyranosides
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Novel photolabile sugar derivatives bearing a 4- or 6-O-(o-nitro)benzyl group have been prepared from the corresponding methyl 4,6-O-(o-nitro)benzylidene α-d-glycopyranosides. Regioselective cleavage with BF3·Et2O/Et3SiH led to the methyl 6-O-(o-nitro)benzyl gluco- and manno-α-d-glycopyranosides 3 and 6. Inversion of configuration at 4-OH position of gluco and manno derivatives offered the otherwise inaccessible methyl 6-O-(o-nitro)benzyl galacto- and talo-α-d-glycopyranosides 4, 5, and 7. Careful reaction with PhBCl2/Et3SiH (3 equiv of reagents, 10 min at -78 °C) led to the desired methyl 4-O-(o-nitro)benzyl gluco- and manno-α-d-glycopyranosides 8 and 9 in very good yield. However, prolonged reaction with 6 equiv of PhBCl2/Et3SiH transformed the methyl 4,6-O-(o-nitro)benzylidene α-d-glucopyranoside 11 into the reduced d-glucitol derivative 15. Oxidative cleavage of 5,6-diol function of 15 gave the corresponding photolabile l-xylose 17. The photolabile glucosides 3 and 8 have been further transformed into the photolabile α-C-allyl d-glucopyranosides 20 and 22.
- Zhu, Chen-Jiang,Yi, Hua,Chen, Guo-Rong,Xie, Juan
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p. 10687 - 10693
(2008/12/23)
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- An iodocyclization approach toward diastereoselective synthesis of highly functionalized tetrasubstituted tetrahydrofurans with 2,5-trans and 2,5-cis relationships from pyranoside derived acyclic oximes
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An efficient method to obtain novel tetrasubstituted tetrahydrofurans with C2 and C5 substitution in trans- and cis-relative configurations has been reported.
- Kumar, Vikas,Gauniyal, Harsh Mohan,Shaw, Arun K.
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p. 2069 - 2078
(2008/02/11)
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- Mild and efficient method for the cleavage of benzylidene acetals using HClO4-SiO2 and direct conversion of acetals to acetates
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HClO4-SiO2 has been used successfully for the deprotection of benzylidene acetals and the direct conversion of benzylidene acetals to the corresponding di-O-acetates. The reactions are very fast and yields are excellent.
- Agnihotri, Geetanjali,Misra, Anup Kumar
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p. 3653 - 3658
(2007/10/03)
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- An investigation into the synthesis of some molecules related to methyl acarviosin
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Methyl acarviosin is an impressive inhibitor of some glycoside hydrolases that process substrates containing α-D-glucosidic linkages. In an attempt to provide putative inhibitors for enzymes that process β-D-glucosidic linkages, we report an improved synthesis of a hydroxylated 'methyl β-acarviosin' and our efforts towards various deoxygenated versions of methyl β-acarviosin. As well, the synthesis of a 1,3-linked variant of methyl β-acarviosin is reported, together with an unsuccessful 'tether' approach to construct the crucial nitrogen linkage in the acarviosins.
- McDonough, Matthew J.,Stick, Robert V.,Tilbrook, D. Matthew G.,Watts, Andrew G.
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p. 233 - 241
(2007/10/03)
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- Cyclic di-t-butylsilylenediyl ether group as a convenient protective group for the glycoconjugate synthesis
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Treatment of methyl β-D-glucopyranoside, methyl α-D-glucopyranoside, 2-azido-2-deoxy-β-D-galactopyranosyl fluoride, and 1,6-anhydro-β-lactose with di-t-butyldichlorosilane gave the corresponding 4,6-cyclic di-t-butylsilylenediyl ether (4,6-CDBS) derivatives in high yields. It was suggested that the 4,6-CDBS group is quite stable under general conditions for further chemical manipulations such as the acetylation, benzylation and glycosylation reactions employed widely in the carbohydrate chemistry. This protective group was readily removed by treatment with tetrabutylammonium fluoride or triethylamine-3HF complex under mild conditions.
- Kumagai, Daijyu,Miyazaki, Masaki,Nishimura, Shin-Ichiro
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p. 1953 - 1956
(2007/10/03)
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- Synthesis of a novel sialyl lewis X analogue containing a pyrrolidine in place of N-acetyl glucosamine 1
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The synthesis of the new sialyl Lewis X analogue, 4-O-(α-L-fucopyranosyl)-3-O-(3-O-sodium sulfonato-β-D-galactopyranosyl)-(2S,3R, 4R)-2-ethyl-3,4-dihydroxypyrrolidine 2 has been achieved. The N-acetyl glucosamine unit of natural Lewis X has been replaced by a rigid 3R/4R-dihydroxylated pyrrolidine 12. This one has been synthezised from the methyl 4-O-benzoyl-2,3-di-O-benzyl-6-deoxy-6-iodo-α-D-altropyranoside sugar precursor 10 using the Ganem/Bemotas one-pot elimination-reductive amination ring contraction reaction. The (2S,3R,4R)-1-benzyloxycarbonyl-3,4-dihydroxy-2-ethylpyrrolidine 12 obtained was subsequently regioselectively glycosylated, using 2,3,4-tri-O-benzyl-α-L-fucopyranosyl fluoride and 2,3,4,6-tetra-O-benzoyl-β-D-galactopyranosyl bromide as glycosyl donors. Disaccharide containing pyrrolidine 21 was finally transformed into the target O-sulfated analog 2, after regioselective sulfation and usual deprotection.
- Dechaux, Elsa,Savy, Pascal,Bouyain, Samuel,Monneret, Claude,Florent, Jean-Claude
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p. 485 - 501
(2007/10/03)
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- O-sulfated derivatives of glucuronic acid
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4-O-Substituted D-glucuronic acid derivatives were synthesized from D-glucose in order to study the regioselectivity of sulfation.
- Castro, Mariano J. L.,Salmaso, Natalia,Kovensky, Jose,Fernandez Cirelli, Alicia
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p. 600 - 601
(2007/10/03)
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- Synthesis of rhamnogalacturonan I oligosaccharides: Synthesis of a tetrasaccharide intermediate
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A hydroxyl protected tetrasaccharide intermediate, corresponding to a segment of the rhamnogalacturonan I polysaccharide, has been synthesized using the glycosyl imidate technique. This tetrasaccharide is designed to allow for further elongation and branching.
- Rich, Jamie R.,McGavin, Robert S.,Gardner, Rebecca,Reimer, Kerry B.
-
-
- NON-PEPTIDE PEPTIDOMIMETICS
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Compounds are provided which are crossreactive with peptides such as those which bind G-protein-linked receptors, together with preparative and therapeutic methods therefor. The compounds have the general structure: STR1 wherein at least one of R 1, R 2, R. sub.3, R. sub.4, or R 5 comprises a functional group which is chemically similar to that found in the peptide of interest.
- -
-
-
- Analysis of the binding specificities of oligomannoside-binding proteins using methylated monosaccharides
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The binding specificities of the closely related lectins from Canavalia ensiformis and Dioclea grandiflora were examined using specifically O-alkylated mono- and disaccharides. Both lectins accept any substitution at the monosaccharide C2 hydroxyl group. The binding energy of C2-alkylated ligands-concanavalin A complexes increases by 1 kcal mol-1 for the C2-O-ethyl ligand, while the binding energies of the corresponding complexes with the Dioclea lectin are identical. Both lectins accept methyl, but not ethyl, substitution of the C3 hydroxyl, in contrast to earlier reports. The results are interpreted in terms of existing models of the concanavalin A binding site. While the results are consistent with a model of the concanavalin A extended binding site that places the non-reducing terminus of all disaccharides in the monosaccharide binding site, they point to the dangers of interpreting the binding behavior of unnatural saccharide ligands on the basis of crystallographic data obtained with native ligands.
- Chervenak, Mary C.,Toone, Eric J.
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p. 1963 - 1977
(2007/10/03)
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- REGIOSELECTIVE FORMATION OF DI-O-BENZYL-SUBSTITUTED HEXOPYRANOSIDES VIA STANNYLENE ACETAL INTERMEDIATES
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The reactions of dibutylstannylene acetals derived from several methyl hexopyranosides with benzyl bromide have been investigated.These reactions occur readily in benzyl bromide at 85 deg C.At reaction times of one to two days, the major products are di-O-benzyl derivatives.In several cases, single di-O-benzyl derivatives are the predominant products: methyl α-D-glucopyranoside and methyl β-D-galactopyranoside gave the 2,6- and 3,6-di-O-benzyl ethers in 82 and 70percent yields, respectively.The species present in these reactions and the reaction pathway are discussed.
- Qin, Huiping,Grindley, T. Bruce
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p. 475 - 490
(2007/10/02)
-
- De novo design and synthesis of somatostatin non-peptide peptidomimetics utilizing β-D-glucose as a novel scaffolding
-
Non-peptide peptidomimetics of the peptide hormone somatostatin (SRIF) were designed and synthesized, utilizing β-D-glucose as a novel scaffolding. Such compounds resemble conventional peptide analogs in that they retain critical amino acid side chains bu
- Hirschmann, Ralph,Nicolaou,Pietranico, Sherrie,Leahy, Ellen M.,Salvino, Joseph,Arison, Byron,Cichy, Maria A.,Grant Spoors,Shakespeare, William C.,Sprengeler, Paul A.,Hamley, Peter,Smith III, Amos B.,Reisine, Terry,Raynor, Karen,Maechler, Laurie,Donaldson, Cindy,Vale, Wylie,Freidinger, Roger M.,Cascieri, Margaret R.,Strader, Catherine D.
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p. 12550 - 12568
(2007/10/02)
-
- Total Synthesis of Antibiotic Hygromycin A
-
The first total synthesis of the antibiotic (-)-hygromycin A (1) has been achieved by a coupling reaction of the sugar moiety (2) and the cyclitol moiety (3).Both components were synthesized in homochiral forms starting from D-glucose.This synthesis fully
- Chida, Noritaka,Ohtsuka, Masami,Nakazawa, Keiichi,Ogawa, Seiichiro
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p. 2976 - 2983
(2007/10/02)
-
- Synthesis of sorbistin analogues.
-
D-Galactose was converted into the glycosylating agents 4-azido-2,3-di-O-benzyl-4-deoxy-6-O-propionyl-alpha-D-glucopyranosyl chloride (11) and the methyl beta-D-thiopyranoside 19. Condensation of 11 with 2,5-diazido-1,6-di-O-benzoyl-2,5-di-deoxy-L-iditol in the presence of mercury salts gave 24% of 2,5-diazido-3-O-(4-azido-2,3-di-O-benzyl-4-deoxy-6-O-propionyl-alp ha-D- glucopyranosyl)-1,6-di-O-benzoyl-2,5-dideoxy-L-iditol. Methyl trifluoromethanesulfonate-promoted glycosylation of 1,3-diazido-2-O-benzyl-1,3-dideoxy-5,6-O-isopropylidene-D-gulit ol with 19 in the presence of 2,6-di-tert-butyl-4-methylpyridine gave 1,3-diazido-4-O-(4-azido-2,3-di-O-benzyl-4-deoxy-6-O-propionyl-alp ha-D- glucopyranosyl)-2-O-benzyl-1,3-dideoxy-5,6-O-isopropylidene-D-gulitol (42), whereas, in the absence of base, migration of the O-isopropylidene group occurred, affording 1,3-diazido-6-O-(4-azido-2,3-di-O-benzyl-4-deoxy-6-O-propionyl-alp ha-D- glucopyranosyl)-2-O-benzyl-1,3-dideoxy-4,5-O-isopropylidene-D-gulitol in addition to 42.
- Medgyes,Jerkovich,Kuszmann,Fuegedi
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p. 225 - 239
(2007/10/02)
-
- Synthesis of 2-Acetoxy-4-formylphenyl 2,3-Di-O-acetyl-6-deoxy-β-D-arabino-5-hexulofuranoside, Structure Confirmation of the Anomeric Configuration of Antibiotic Hygromycin A
-
2-Acetoxy-4-formylphenyl 2,3-di-O-acetyl-6-deoxy-β-D-arabino-5-hexulofuranoside, one of the degradation products of antibiotic hygromycin A, was synthesized.The present study confirmed the anomeric configuration of the antibiotic to be "β".
- Chida, Noritaka,Ohtsuka, Masami,Ogawa, Seiichoro
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p. 969 - 972
(2007/10/02)
-
- Gas Phase Glycosidic Cleavage of Oxyanions from Alkyl Glycosides
-
The oxanions - from several methylglycosides were generated by fast atom bombardment and their decomposition was studied by mass-analysed ion kinetic energy spectrometry.The main decomposition pathway is the loss of methanol.The hydroxylic
- Prome, Jean-Claude,Aurelle, Helene,Prome, Danielle,,Savagnac, Ariette
-
-
- Synthesis from D-Glucose of 1,5-Dideoxy-1,5-imino-L-fucitol, a Potent &α-L-Fucosidase Inhibitor
-
1,5-Dideoxy-1,5-imino-L-fucitol (1), sythesised from methyl α-D-glucopyranoside, is a potent competitive inhibitor of the hydrolysis of p-nitrophenyl α-L-fucopyranoside catalysed by α-L-fucosidase (ex. bovine epididymis) causing 50percent inhibition of en
- Fleet, George W. J.,Shaw, Antony N.,Evans, Stephen V.,Fellows, Linda E.
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p. 841 - 842
(2007/10/02)
-
- SYNTHESIS OF METHYL ETHERS OF URONIC ACIDS. III. SYNTHESIS OF METHYL (METHYL-α-D-MANNOPYRANOSID)URONATE AND ITS 2- AND 4-O-METHYL ETHERS
-
The synthesis of methyl (methyl α-D-mannopyranosid)uronate and its 2- and 4-O-methyl ethers has been effected by the chromium trioxide oxidation of the corredponding O-benzyl and O-benzylidene derivatives of methyl α-D-mannopyranoside, esterification with
- Grishkovets, V. I.,Zemlyakov, A. E.,Chirva, V. Ya.
-
p. 401 - 403
(2007/10/02)
-
- Syntheses of model oligosaccharides of biological significance. Synthesis of methyl 3,6-di-O-(alpha-D-mannopyranosyl)-alpha-d-mannopyranoside and the corresponding mannobiosides.
-
Methyl 2-O-allyl-4,6-O-benzylidene-3-O-(2,3,4,6-tetra-O-acetyl-alpha-D-mannopyranosyl) -alpha-D-mannopyranoside (12) was prepared in 90% yield by Helferich glycosylation of methyl 2-O-allyl-4,6-O-benzylidene-alpha-D-mannopyranoside (9) with tetra-O-acetyl
- Winnik,Brisson,Carver,Krepinsky
-
-
- Preparation of two methyl deoxyfluoro-beta-D-galactopyranosides, and their interaction with galactan-specific immunoglobulin A J539 (Fab').
-
Methyl 2-deoxy-2-fluoro-beta-D-glactopyranoside (2) and methyl 4-deoxy-4-fluoro-beta-D-glactopyranoside (7) have been prepared, and the possibility of their binding to (1 leads to 6)-beta-D-galactopyranan-specific immunoglobulin A J539 (Fab') has been investigated. Compound 2 does not show binding, whereas 7 does. It appears that the 2-hydroxyl group of methyl beta-D-galactopyranoside may take part in hydrogen bonding to the protein.
- Ittah,Glaudemans
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p. 189 - 194
(2007/10/02)
-
- Bausteine von Oligosacchariden, XXII. Synthese der Trisaccharid-Sequenz α-D-GlcNAc-(1-4)-β-D-Gal-(1-4)-D-GlcNAc aus blutgruppenaktiven Substanzen
-
A directly stereoselective α-glycoside synthesis to oligosaccharides succeeds in the presence of AgClO4/Ag2CO3 in methylene chloride with the α-bromide 1 of 2-azido-2-desoxy-D-glucose.By reaction with 1 the disaccharides 3, 7a, 7b, 18 and the trisaccharid
- Paulsen, Hans,Schnell, Dagmar
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p. 333 - 345
(2007/10/02)
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- Syntheses and 1H- and 13C-Nuclear Magnetic Resonance Spectra of All Positional Isomers of Methyl Mono-O-tetradecanoyl-α- and β-D-Glucopyranosides
-
All the isomers of the mono-O-myristoyl derivative of methyl α- and β-D-glucopyranosides were unambiguously prepared, and their 1H- and 13C-NMR spectra are discussed in relation to the stereochemistry of the pyranose ring and ester grouping.The acylation
- Yoshimoto, Kimihiro,Itatani, Yoshitaka,Shibata, Kanoko,Tsuda, Yoshisuke
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p. 208 - 219
(2007/10/02)
-