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McCloskey, and G. Coleman, Org. Perrie, J. Harding, C. King, D. Sinnott, and A. Stachulski, Org. Nicolaou, J. Li, and G. Zenke, Helv. Acta 83, Paulsen, J. Boons, and A. Demchenko, Chem Rev. Paulsen, and H. Tietz, Carbohydr. Maeda, K. Ito, H. Ishida, M. Hasegawa, J. Sugiyama, and J. Diakur, Organic Lett. Kahne, S. Walker, Y. Cheng, and D. Van Engen, J. Plante, and P. Seeberg, J.
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Nicolaou, T. Ohshima, F. Vourloumis, J. Xu, J. Pfefferkorn, and S. Kim, J. Kitagawa, K. Ohashi, N. Baek, M. Sakagami, M. Yoshikawa, and H. Shibuya, Chem. Ellervik, and G. Magnusson, J. Crich, and H. Cross, and D. Koviak, M. Chapell, and R. Halcomb, J. Wong, X. Ye, and Z. Zhang, J. Lakhmiri, P. Lhoste, and D. Sinou, Tetrahedron Lett. Chaudhary, and O. Hart, D.
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Synthesis and Characterization of Glycosides | Marco Brito-Arias | Springer
Seeberger, Chem. General examples of O-glycosides are shown in Figure 2. Examples of O-glycosides. O-glycoside chromophores used for enzymatic detection. This reaction has been employed for the preparation of O-glycosides that are used as substrates for detection and measurement of enzymatic activity of most of the known glycosidases. Using this methodology, several chromophores have been attached to most of the common monosaccharides. After O-glycoside cleavage by the enzyme, the release of the chromophore will indicate the sites and eventually will quantify the enzymatic activity.
Some of the chromophores currently used for these purposes are represented in Figure 2. CH2 Cl2, r. Michael approach for preparation umbellyferyl-O-glycoside. This straightforward strategy is used specially for the preparation of simple Oglycosides. The advantage of this methodology is that it does not require the use of protecting groups and simply by combining the free sugar with an alcohol under acidic condition we furnish the corresponding O-glycoside. However, contrary to the previous method, this procedure is not stereo selective and therefore it provides a mixture of anomers.
Also, it has been found satisfactory only for small aliphatic alcohols Figure 2. The addition of a controlled stream of dry HCl during a period of around 10 min at room temperature generally are the conditions of choice. Synthesis of indole O-glycoside derivative. NAc 72 2.
The Fischer glycoside reaction. It is also seen that the amount of these isomers depends importantly on the condition reactions employed Figure 2. The Fischer methodology has been applied successfully for the synthesis of benzyl O-glycosides. The Fischer O-glycoside isomers. Fischer conditions for preparation of Benzyl L-fucose. General Methods 73 2. CH2 Cl2 , r. This reaction reported in is still one of the most useful reactions for preparing a wide variety of O-glycosides. Also a drying agent such as calcium sulfate drierite , calcium chloride, or molecular sieves is recommended.
Improved yields are obtained with iodide, vigorous stirring, and protection against light during the course of the reaction. The stereochemistry observed is 1,2 trans type in most of the cases reported, as a consequence of neighboring group participation. When the protecting group is acetate at C 2 , there is an intramolecular nucleophilic displacement of the leaving group, generating an orthoester.
Only until recently a method for preparing 1,2-cis glycosides has been developed involving the use of 1S -phenyl phenylsulfanyl ethyl moiety at C-2 of a glycosyl donor to give a quasi-stable anomeric sulfonium ion. The sulfonium ion is formed as a transdecalin ring system. The Koenigs-Knorr reaction. Proposed mechanism for the Koenigs-Knorr glycosidic reaction. The synthesis of various disaccharides containing N-acetylneuraminic acid Neu5Ac was achieved by using acetochloro and acetobromo neuraminic acids as glycosyl donors with active glycosyl acceptors under Ag2 CO3 -promoted reactions conditions Figure 2.
Synthesis of steroidal glycoside. Synthesis of a steroidal O-glycoside. Synthesis of gentobiose. Synthesis of laminaribiose. Synthesis of tetrasaccharide. Also, more polar solvents are used such as acetonitrile or nitromethane Figure 2. However, a mixture of anomers is often observed. By following this strategy, Umezawa et al. The catalyst employed was mercury II cyanide Figure 2. Other coupling reactions between sugars under Helferich conditions have been as well described.
Glycosilation reaction for preparation of Bleomycin precursor. The Helferich general reaction. Synthesis of a kanamacin A derivative. Synthesis of Epirubicine. Helferich conditions for the preparation of sialic disaccharide. Also aromatic S-glycosides could be effectively prepared under the fusion method. Naphtyl O-glycosides and Phenyl S-glycosides. This strategy involves the use of trichloroacetonitrile that in the presence of a base is incorporated on the anomeric hydroxyl group to generate trichloroacetimidate Figure 2. It should be noted that the resulting imidate derivative is air- sensitive and should be used in coupling reactions immediately following preparation.
The use of a catalyst such as BF3. Although the unquestionable applicability of this approach, an undesirable side reaction has been encountered with glycosyl trichloroacetimidates in the presence of Lewis acid catalysis via the Chapman rearrangement. Preparation of glycosyl imidate and 1 H NMR of imidate ramnosyl derivative.
OEt2 as Lewis acid catalyst Figure 2. Naturally occurring herbicides known as tricolorin A, F, and G were isolated from the plant Ipomea tricolor and since then synthesized involving glycoside coupling reactions.
Pdf Synthesis And Characterization Of Glycosides 2006
The lactonization key step for the preparation of the synthesized tricolorins has been achieved either under macrolactonization conditions reported by Yamaguchi26,27 and also under ring clousure methathesis conditions. Nucleophilic displacement of imidate leaving group. Coupling reaction for the preparation of ganglioside. Another hetero-trisaccharide resin glycoside of jalapinolic acid known as tricolorin F has been synthesized involving coupling reactions with imidates as glycosyl donors.
In this way disaccharide and trisaccharide were prepared sequentially. The resulting tricoloric acid C derivative was deprotected and subjected to lactonization under Yamaguchi conditions to produce protected macrolactone. Final removal of acetonide and benzyl protecting groups provided Tricolorin F Figure 2. Glycosylation of calicheamicinone congener. OEt2 , furnished the tumoral fragment Lewis X Figure 2. Selectins E,P and L are mammalian C-type lectins involved in the recognition process between blood cells or cancer cells and vascular endothelium.
Synthesis of tricolorin A precursor. Synthesis of Tricolorin F. OEt2, CH2Cl2. Covergent synthesis of Lewis X fragment. N3 OBn 88 2. Coupling reaction for the preparation of Lewis x pentasaccharide intermediate. Likewise, thioaryl donors can also be suitably converted to acetimidates for performing glycoside coupling reactions.
This strategy has been succesfully applied in the syntheses of cytotoxic marine natural products Eleutherobin Figure 2. Et2 O, r. CH2 Cl2, MS, r. An example of their applicability for the preparation of saccharide synthesis is represented in Figure 2. Thioalkyl donor are also useful derivatives for the preparation of biologically important natural sugars known as Sialic acids. O-glycosilation reaction proceeds between the thioglycosylsialic donor with a glycosyl acceptor bearing an -OH group available , using a catalyst such as N-iodosuccinimide-TfOH as promotor Figure 2.
Citotoxic marine glycoside Eleutherobin. H2O, EtOH reflux. Thioglicoside coupling reaction for preparation of a trisaccharide intermediate. Synthesis of an antigen polysaccharide fragment. Thioalkyl donor for the preparation of sialic acids. Convergent synthesis of sialyl oligosaccharide. These conditions were applied for preparing Salmonella-type E1 core trisaccharide Figure 2.
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Thus, disaccharide formation under glycosidic conditions provided the disaccharides in high yields Figure 2. General scheme for the armed-disarmed approach. The resulting disaccharide now becomes an armed disaccharide, which in turn is reacted with another glycosyl acceptor or disarmed sugar to produce the oligosaccharide chain elongation Figure 2. As one can see, the disarmed sugar intermediates function as glycosyl acceptor bearing the hydroxyl group at position 6 available for establishing a glycosidic linkage with the armed unit. Despite the usefulness of pentenyl as protecting group, clear preference in the use of thioglycoside donors as armed and disarmed donors is often observed Figure 2.
The armed-disarmed approach. The general scheme of the armed-disarmed approach with thioglycosyl sugars. Preparation of Lewis X tetrasaccharide using armed-disarmed coupling method. Recently S-benzoxazol thio glycoside SBox was synthesized and introduced as alternative glycosyl donor for preparing disaccharides under the armed-disarmed approach.
Thus, the SBox glycosyl donor was used as armed donor and condensed with disarmed thioglycoside to provide the target disaccharide Figure 2. SPh 98 R2 2. Armed-disarmed synthesis using S-benzoxazol SBox as disarmed glycosyl donor. These useful intermediates were discovered by Fischer and Zach in and their utility in the preparation of building blocks for oligosaccharide synthesis is increasingly important. Different routes for the preparation of triacetyl glycals have been examined by Fraser-Reid et al.
Moreover, a suitable one-pot preparation of glycals has been more recently described, starting from reducing sugars by Shull et al. The completion of this reaction can be followed by 1 H NMR, where the presence of a signal around 6. As for any double bond, these unsaturated sugars may undergo electrophilic addition, which takes place at the C2 position leaving a positive charge at C1, which instantly reacts with the conjugate base.
This reaction is particularly useful for the preparation of 2-deoxypyranosides Figure 2. Electrophilic addition. The Brigl epoxide formation. A more extended application for glycoside bond formation has been developed recently. The oxidation of the double bond has been successfully achieved with dimethyl dioxirane DMDO in acetone Figure 2. The concentrations of DMDO are in the order of 0. Likewise, alternative epoxide conditions from glycals have been assayed besides DMDO treatment.
The resulting glucal disaccharide generated as a single coupling product was further converted to the epoxide, which eventually led to the next coupling reaction with another glucal acceptor Figure 2. The tetrasaccharide Cap domain of the antigenic lipophosphoglycan of Leishmania donovani has been prepared under the glycal approach by Upreti and Vishwakarma.
This was coupled to the mannobiose donor to produce the tetrasaccharide, which after deprotecction led to the tetrasaccharide Cap domain Figure 2. General procedures for preparation of glycosidic bond of glycopeptides can be reviewed in the comprehensive study reported by Kunz. O OH 2. Alternative glycal-epoxidations. Epoxide glycal as glycosil donors. Synthesis of a tetrasacharide using an epoxide disaccacharide as glycosyl donor.
Synthesis and Characterization of Glycosides
Amino acids glycosidation. O-Glycoside Formation This methodology has been extended for the preparation of E-selectin ligand tetrasaccharide sialyl Lewisx SLex , which is located at the terminus of glycolipids present on the surface of neutrophils. Sulfated Lex and Lea -type oligosaccharide selectin ligands were synthetically prepared as described below.
Chemoenzymatic synthesis of tetrasaccharide sialyl Lea. The sulphated tetrasaccharide was formed by reaction of tetrasaccharide acceptor with SO3. NM3 complex in anhydrous pyridine Figure 2. Fluorine monosaccharide as glycosyl donor. OEt2, Et2O, r. Total synthesis of sulphated Lex. OH OH 2. Silyl derivatives as glycosyl donors. Silyl groups are best known as versatile protecting groups, and their use as leaving groups for glycoside bond formation has been more limited. An example of glycoside formation involving a silyl group as leaving group is reported for the preparation of luganol O-glycoside.
It is worth mentioning that stereoselectivity is dependent on C-2 neighboring group participation. The use of selenoglycosides as glycosyl donors and acceptor in glycosilation reactions has also been described by Metha and Pinto. Tetrazol has also been tested as a leaving group for the preparation of an antibiotic fragment. Phenylselenosugars as glycosyl donors.
The use of tetrazol as a leaving group. Sigmatropic rearrangement. OMe 2. Glycosylation reaction for preparation of Arthrobacilin A. Stereocontrolled O-glycosidations using heterogeneous polymeric materials. These donors have been used for the preparation of sialyl oligosaccharides; however, the yield reported were moderate. This is the case of the preparation of sialyl tetrasaccharide derivative, which was carried out by condensation 2. Phosphorous glycosyl donors for oligosaccharide synthesis.
Besides there is a current need of developing economical and environmentally friendly processes for synthesis. Glycosyltransferases are important enzymes involved in essential processes related to oligosaccharide biosynthesis, and they have been found also very useful as biocatalyst for the chemoenzymatic synthesis of interesting oligosaccharides 2. Glycosylation with galactosyltransferases. Glycosylations with galactosyltransferases can be performed through the use of glucosephosphate as donor. Synthesis of silayl trisaccharide mediated by silayl glycosiltransferase.
Enzymatic synthesis of ganglioside. This cofactor was regenerated with lactate dehydrogenase in the presence of piruvate Figure 2. Enzymatic preparation of glucosamine 6- and 1-phosphate. Enzymatic preparation of UDP-glucuronide. Synthesis of CMP-N-acetylneuraminic acid. Glycosynthase-catalyzed oligosaccharide synthesis. The proposed mechanism of glycosynthase-catalyzed reaction is illustrated in Figure 2. In the general procedure illustrated in Figure 2. Example of microbial catalyzed coupling reaction. Transglycosylation reaction for the preparation of 2- and 3-linked trisaccharides. Transfer of the sulfuryl group from PAPS to the glycoside.
Chemoenzymatic synthesis of rhodiooctanoside. Enzymatic synthesis of lactosamine. O-Glycoside Formation wall cells and are usually in the form of glycopeptides. Different types of monosaccharides can be present as constitutive parts such as glucose, galactose, mannose, N-acetylglucosamine, silaic acid, and L-fucose. Also, the order of linkage and stereoselectivity between them is rarely conserved. The solid-phase approach involves three elements, namely the glycosyl donor, glycosyl acceptor, and the resin, which is properly activated with a group susceptible for attachment either with the glycosyl donor or acceptor depending on the strategy of choice.
Although it appears obvious, it is important to remain that the linkage between the resin and the sugar should be easily cleaved under compatible conditions for the glycoside bond. One general approach involves the initial attachment of a glycosyl donor halides, trichcloroacetimidate, sulfoxides, phosphates, phosphates, thio and pentenyl and glycols to the resin polystyrene-base.
The attached sugar is selectively deprotected depending on the required position 1,2- 1,3- 1,4- 1,6 , transforming the resin-sugar complex in a sugar acceptor which will be coupled to the next glycosyl donor to produce a second linkage. By repeating this sequence an elongated chain is obtained. Suitable hydroxyl group from the donor will serve as linkage site with de next sugar unit for chain elongation. It should be noted that the glycosyl donor also contains a position available for the linkage with the next sugar. In other words, the glycosyl donor once attached to the resin becomes a glycosyl acceptor, as can be seen for the next coupling sequence Figure 2.
The glycosyl donor chosen was acetobromoglucose functionalized with trichloroacetate group as a temporary protecting group at position 5. Glycosylation reactions were effected under Helferich conditions and cleavage from resin was performed with hydrazinium acetate Figure 2. The 2. General scheme for solid-phase oligosaccharide synthesis 1,4-linkage case.
The enzymatic solid-phase oligosaccharide synthesis relies mainly by the use of glycosyltransferases, glycosidases and glycosynthases. By taking advantage on their high stereo- and regioselectivity, various oligosaccharides and glycopeptides have been prepared usually under mild conditions without the need of using protecting groups. Example of donor-bound strategy for solid-phase glycosilation reactions. Sulfur mediated solid-phase coupling reaction. Two general approaches have been proposed for the preparation of oligosaccharides through the solid-phase approach Figure 2.
Final treatment with hydrazine was used to release the tetrasaccharide from the solid support Figure 2. Solid-phase coupling promoted by Helferich conditions. OH 2. There are two main approaches proposed based on the cycloglycosylation step. Nowadays the industrial production of cyclodextrins relies on the enzymatic conversion of prehydrolyzed starch into a mixture of cyclic and acyclic oligomers.
A full report about cyclic oligosaccharides90 proposes four approaches to the synthesis of cyclic oligosaccharides developed during the last 10 years: 1. Two general approaches for immobilized solid-phase oligosaccharide synthesis. Enzymatic-solid phase glycosylation reaction. The four suggested approaches to the synthesis of cyclic oligosaccharides. As can be seen in Figure 2. OAll 2. Br 2. Enzymatic synthesis of cycloinulooligosaccharides. Toshima, and K. Tatsuta, Chem. Anderson, and D. Leaback, Tetrahedron 12, Wessel, Carbohydr. Shearly, C. Amett, J. Igarashi, Adv.
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Hanessian, M. Tremblay, and E. Swayze, Tetrahedron, 59, Tanaka, Y. Nishida, Y. Furuta, and K. Kobayashi, Bioorg. Roth and A. Kleeman, Pharmaceut. Suami, T. Otake, T. Nishimura, and Y. Ikeda, Bull. Bagget, A. Samra, and A. Smithson, Carbohydr. Schmidt, and K. Jung, Carbohydr. Schmidt and W. Kinzy, Adv. Hasegawa, K. Fushimi, H. Ishida, and M. Kiso, J. Danishefsky and M. Shair, J. Larson, C. Lu, Q. Guo, B. Yu, and Y. Hui, J. Brito-Arias, R. Pereda-Miranda, and C. Boons, S. Isles, J. Boons, Contemporary Organic Synthesis 3, Komba, H. Galustian, H.
Ishida, T. Feizi, R. Kannagi, and M. Kiso, Angew. Zhang, A. Brodsky, P. Sinay, Tetrahedron: Asymmetry 9, Ito, and H. Ishida, Kiso J. Koenig, R. Jain, R. Vig, K. Norgard,-Sumnicht, K. Matta, and A. Varki, Glycobiology, 7, 79 Sanders, E. Gordon, O. Dwir, P. Beck, R. Alternate Sources. Save to Library. Create Alert. Share This Paper. Citations Publications citing this paper.
Regioselective mono-etherification of vicinal diols using tin II halide catalysts and diazo compounds Sean Michael Scully. Effects of pre and post-harvest treatments on the phenolic compounds and antioxidant activity of different onion varieties Feiyue Ren. Nnadiukwu , Comfort C. Monago-Ighorodje , Lawrence C. Rapid phenolic O-glycosylation of small molecules and complex unprotected peptides in aqueous solvent Tyler J. Targeting BDNF modulation by plant glycosides as a novel therapeutic strategy in the treatment of depression. References Publications referenced by this paper.
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