Synthesis of the methyl umbelliferone derivative of the type 2 blood group a. Synthesis of trisaccharide methyl glycosides related to fragments of the capsular polysaccharide of streptococcus pneumoniae type 18c augusta m. Use of nah as base for the deprotonation is convenient, but when selective substitution is needed for example, protection of one hydroxyl group. Bocprotected amino groups organic chemistry portal. Practical demethylation of aryl methyl ethers using an. The chemical route involves extremes of temperature, pressure, use of toxic catalysts, and multiple steps of protection, deprotection and activation 11. Pdf a continuous flow procedure for the synthesis of methyl glycosides fischer glycosylation of various. Therefore, the synthesis of oligosaccharides is of considerable interest for biological, medicinal, and pharmacological studies.
Maleczka jr michigan state university, east lansing, mi, usa additional. Alkalipromoted condensation of the carboxylic acid with bromo glycosides was found to be more efficient in the synthesis of 28 glycosides. A facile chemoselective deprotection of anomeric o methyl glycosides has been achieved in good to excellent yields within 10. Commercial production of these surfactants is carried out in multiple steps through fischer glycosylation reactions under.
Vliegenthart bijvoet center, department of bioorganic chemistry, utrecht university, p. Synthesis of the methyl glycosides of a di and two trisaccharide fragments specific for the shigella flexneri serotype 2a oantigen. Cooh28 group, instead of commonly used methyl and allyl, to avoid difficulties in the final deprotection. Prefixes o, s, n and c indicate oxygen, thio, nitrogen or carbon glycosides followed by the name of the aglycon methyl, phenyl, benzyl etc. The diether product is stable to base and alkaline oxidants such as tollens reagent. The chemistry of npentenyl glycosides c manal 781 6 a 2manal\.
It can be prepared in the laboratory by the acidcatalyzed reaction of glucose with methanol it is used as a chemical intermediate in the production of a variety of products including emollients, emulsifiers, humectants, moisturizers, thickening agents, plasticizers, surfactants, varnishes, and resins. The carbohydrate synthesis specialists at synthose. After 1 h of stirring, the mixture had become homogeneous. The anomeric methyl glucosides are formed in an equilibrium ratio of 66% alpha to 34% beta. Sugar chemistry constrained sialic acid donors enable. Jun 27, 2008 a facile chemoselective deprotection of anomeric omethyl glycosides has been achieved in good to excellent yields within 10. Cbz carbamates, azetidine, benzyl and methyl esters, tbdms, and methyl phenyl ethers are tolerated. Regioselective modification of unprotected glycosides. Deprotection of a methyl ester using lioh chembark. A facile chemoselective deprotection of anomeric o methyl glycosides has been achieved in good to excellent yields within 1040 min with use of trityl tetrafluoroborate in dichloromethane at.
However, the preparation of these glycosyl donors requires laborious task including the protection and deprotection of the hydroxy groups and the purification of products. Protecting groupfree synthesis of glycosides tspace university. Synthesis of trisaccharide methyl glycosides related to. Catalytic conversion methyl glycosides with maintaining the intrinsic stereostructure is.
An improved helferich method for the stereoselective. These are extensively used in personal care products, pharmaceutical preparations and membrane protein research. Albr3, etsh phse ph2p me3sii o o obz ome o o obz oh albr 3, etsh tl 1987, 28, 3659 methoxymethyl ether mom roh roch2ome stable to base. Apr, 2008 a highly practical method for demethylation of aryl methyl ethers employing a longchain thiol has been developed. Benzyl ethers can by generated using the williamson ether synthesis, for example, where initial deprotonation of the alcohol and subsequent reaction with benzyl bromide delivers the protected alcohol. Journal of chroinatography, 3 1977 39 d elsevier scientific publishing company, amsterdam printed in the netherlands chrom. The partial methylation of methyl xylo, arabino, lyxo and rhamnopyranosides by purdies method has been studied. Furthermore, these glycosides derivatives were advantageously utilized for optical resolution. Under the conditions described herein, clean and fast conversions to the desired phenolic compounds have been achieved with a broad range of substrates. Figure 2 glycon and aglycon concept and systematic nomenclature of glycosides the common name of a glycoside consists of several parts. Synthesis of ldaunosamine andlristosamine glycosides via. Dimethoxy triazine glycosides as new glycosyl donors for. Some sugar derivatives are sufficiently volatile to be analysed by gas chromatography gc without further derivatization. A facile chemoselective deprotection of anomeric omethyl glycosides has been achieved in good to.
Dglucopyranoside products were measured, which ultimately were not published 6. Aqueous phosphoric acid is an effective, environmentally benign, selective and mild reagent for the deprotection of tertbutyl carbamates, tertbutyl esters, and tertbutyl ethers. Constrained sialic acid donors enable selective synthesis of. Methylglucoside is a monosaccharide derived from glucose. Request pdf mild and efficient chemoselective deprotection of anomeric o methyl glycosides with trityl tetrafluoroborate a facile chemoselective deprotection of anomeric o methyl glycosides. Mild and efficient chemoselective deprotection of anomeric. The selectivity could be inverted by using tetramethylethylenediamine tmeda instead of phbox ligand 20 scheme 6. Catalytic production of chiral polyols using deoxydehydration of methyl glycosides over reoxpdceo2 without protecting oh groups keiichi tomishige school of engineering, tohoku university, sendai, 9808579, japan abstract.
Mild and efficient chemoselective deprotection of anomeric o. Vankar department of chemistry, indian institute of technology kanpur 208 016, india contents list of the supporting information. Aglycone s sugar s glycosides aglycone n sugar n glycosides number of sugars. Churms, in encyclopedia of separation science, 2000. A facile chemoselective deprotection of anomeric omethyl glycosides has been achieved in good to excellent yields within 1040 min with use of trityl tetrafluoroborate in dichloromethane at. Two approaches were investigated and proved practicable in the preparation of 3,28diglycosides. Sialic acid is a sugar residue present in many biologically significant glycans of mammals, commonly as a terminal. Jul 31, 2018 finally, silyl etherprotected crosscoupling products are often inconvenient for further transformation to. Pdf mild and efficient chemoselective deprotection of. Linhardt department of chemistry, medicinal and natural products chemistry and chemical and biochemical engineering, the uni ersity of iowa, iowa city, ia 52242, usa. A similar series of transformations starting from hex2enopyranoside9 would afford.
Po osugar b c 20 i osugar these compounds were readily synthesized by adapting ogawas procedures for the corresponding methyl glycosides. Alkyl glycosides and polyglycosides are environment friendly, nonionic surfactants with favourable properties like biodegradability and chemical stability. Synthesis of the methyl glycosides of a di and two. Although a remarkable variety of heavy metal salts have been reported to successfully promote the koenigsknorr. The present method is easily implemented and tolerates different functional groups. Hydrolysis of the octamethyllactose with dilute acid cleaves the glycosidic linkage joining the two monosaccharides and the methyl glycoside. Mild and efficient chemoselective deprotection of anomeric o methyl glycosides with trityl tetrafluoroborate. Mild and efficient chemoselective deprotection of anomeric o methyl glycosides using trityl tetrafluoroborate amit kumar, venkata ramana doddi and yashwant d. Helferich procedure for the successful glycosylation of 4mu with methyl tetraoacetyl dglucopyranuronate and several other peracetylated sugars to afford the corresponding protected glycosides with high stereoselectivity under mild conditions, followed by deprotection to produce 4methylumberlliferyl glycosides products scheme 1.
Facile synthesis of oleanolic acid monoglycosides and. Both mixtures were chilled to 4 c and combined to form a turbid white mixture. Protecting groupfree synthesis of glycosides caroline emilie paul master of sciences graduate department of chemistry university of toronto 2010 abstract carbohydrates play major roles in many biological processes. Acetals tetrahydropyranylethers it is readily introduced by reaction of the enolether dihyrdopyranwith an alcohol in the presence of an acid catalyst such as tsoh, bf3, pocl3. Schematic showing an ordered selfassembled monolayer of densely packed alkane thiols. Request pdf direct synthesis of unsaturated sugars from methyl glycosides transformation of sugars without protection of the oh groups is an ideal method and a powerful tool for biomass. Partial methylation of methyl glycosides springerlink. Since acidcatalyzed aldolization is reversible, glycosides may be hydrolyzed back to their alcohol and sugar components by aqueous acid. Protectiondeprotection of cyclic carbamate on phenyl ring 1a,b via different methods the compounds 2a,b10a,b,inscheme 1, were synthetized by methods a or b, according the reagent desired, with 23hbenzoxazolone 1aor23hbenzothiazolinone 1b. The chemical structure of sialic acid, which features an anomeric center with carboxyl and methylene substituents, poses a challenge for synthesis of the. Ags can also be prepared enzymatically by glycosidases e. Cglycosides, presumably due to the bulkiness of the protecting groups and for ringstrain reasons.