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1.
Makoto Kiso Yuji Ogawa Yushun Fujishima Minoru Fujita Shinji Tanaka Akira Hasegawa 《Journal of carbohydrate chemistry》2013,32(4):625-638
Abstract In order to elucidate further the relationship between the composition of the fatty acyl groups in the nonreducing-sugar subunit of bacterial lipid A and its biological activity, 3-O-[(3R)-3-(acyloxy)tetradecanoyl]-2-deoxy-2-[(3R)-3-hydroxytetradecanamido]-4-O-phosphono-D-glucose [GLA-63(R, R) and GLA-64(R, R)], and 3-O-[(3R)-3-(acyloxy)tetradecanoyl]-2-deoxy-4-O-phosphono-2-tetradecanamido-D-glucose [GLA-67(R), GLA-68(R) and GLA-69(R)] have been synthesized. Benzyl 2-[(3R)-3-(benzyloxymethoxy)tetradecanamido]-2-deoxy-4,6-O-isopropylidene-β-D-glucopyranoside (5) and benzyl 2-deoxy-4,6-O-isopropylidene-2-tetradecanamido-β-D-glucopyranoside (6) were each esterified with (3R)-3-dodecanoyloxytetradecanoic acid (1), (3R)-3-tetradecanoyloxytetradecanoic acid (2) or (3R)-3-hexadecanoyloxy-tetradecanoic acid (3), to give 7-11, which were then transformed, by the sequence of deisopropylidenation, 6-O-tritylation and 4-O-phosphorylation, into a series of desired compounds. 相似文献
2.
Abstract Glycosylation of methyl 3-O-(2-acetamido-3, 6-di-O-benzyl-2-deoxy-β-D-glucopyranosyl)-2,4,6-tri-O-benzyl-β-D-galactopyranoside (2) with 2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl bromide (1), catalyzed by mercuric cyanide, afforded a trisaccharide derivative, which was not separated, but directly O-deacetylated to give methyl 3-O-(2-acetamido-3,6-di-O-benzyl-2-deoxy-4-O-β-D-galactopyranosyl-β-D-giucopyranosyl)-2,4,6-tri-O-benzyl-β-D-galactopyranoside (8). Hydrogenolysls of the benzyl groups of 8 then furnished the title trisaccharide (9). A similar pflyccsylation of methyl 3-O-(2-acetamido-3-O-acetyl-2-deoxy-β-D-glucopyranosyl)-2,4,6-tri-O-benzyl- β-D-galactopyranoside (obtained by acetylation of 4, followed by hydrolysis of the benzylidene acetal group) with bromide 1 gave a tribenzyl trisaccharide, which, on catalytic hydrogenolysls, furnished the isomeric trisaccharide (12). Methylation of 4 and 2 with methyl iodide-silver oxide in 1:1 dichloro-methane-N, N-dimethylformamide gave the 3-O- and 4-O-monomethyl ethers (13) and (15), respectively. Hydrogenolysis of the benzyl groups of 13 and 15 then provided the title monomethylated disaechartdes (15) and (16), respectively. The structures of trisacchacides 9 and 12, and disaccharides 14 and 16 were all established by 13C MMR spectroscopy. 相似文献
3.
Akira Hasegawa Masahiko Ozaki Makoto Kiso Ichiro Azuma 《Journal of carbohydrate chemistry》2013,32(2):331-341
Abstract N-[2-S-(2-Acetamido-2,3-dideoxy-D-glucopyranose-3-y1)-2-thio-D-lactoyl]-L-alanyl-D-isoglutamine, in which the oxygen atom at C-3 of N-acetylmuramoic acid moiety in N-acetylmuramoyl-L-alanyl-D-isoglutamine (MDP) has been replaced by sulfur, was synthesized from allyl 2-acetamido-2-deoxy-β-D-glucopyranoside (1). Treatment with sodium acetate of the 3-O-mesylate, derived from 1 by 4,6-O-isopropylidenation and subsequent mesylation, gave allyl 2-acetamido-2-deoxy-4,6-O-isopropylidene-β-D-allopyranoside (4). When treated with potassium thioacetate, the 3-O-mesylate, derived from 4, afforded allyl 2-acetamido-3-S-acetyl-2-deoxy-4,6-0-isopropylidence-β-D-glucopyranoside (6). S-Deacetylation of 6, condensation with 2-L-chloropropanoic acid, and subsequent esterification, gave the 3-s[D-1(methoxycarbonyl)ethyl]-3-thio-glucopyranoside derivative (7). Coupling of the acid, derived from 7, with the methyl ester of L-alanyl-D-isoglutamine, and subsequent hydrolysis, yielded the title compound. 相似文献
4.
Irwin G. Leder 《Journal of carbohydrate chemistry》2013,32(3):583-592
Abstract Starting with methyl 2-(benzyloxycarbonyl)amino-2-deoxy-α-D-glucopyranoside (1), the isomeric methyl 2-amino-2-deoxy-α-D-glucopyranoside 3-, 4-, and 6-sulfates have each been prepared by sulfation of suitably blocked intermediates. Tritylation and acetylation of 1 followed by detritylation gave methyl 3,4-di-0-acetyl-2-(benzyloxycarbonyl)amino-2-deoxy-α-D-glucopyranoside (3), having a free 6-hydroxyl group. Base catalyzed 0–4→0–6 acetyl migration provided the corresponding 3,6 di-O-acetyl derivative (4) posessing a free 4-hydroxyl group. Preparation of methyl 4,6-0-benzylidene-2-(benzyloxycarbonyl)amino-2-deoxy-α-D-glucopyranoside (9) provided the intermediate bearing a free 3-hydroxyl group. 0-sulfation of 3, 4, and 9 was effected with the pyridine sulfur trioxide complex in dry pyridine. 相似文献
5.
Abstract Different reaction conditions were investigated for the preparation of benzyl 2-acetamido-3,6-di-O-benzyl-2-deoxy-β-D-glucopyranoside (5). Compound 5 on reaction with 2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl bromide afforded the 4-O-substituted 2-acetamido-2-deoxy-β-D-glucopyranosyl derivative which, on O-deacetylation, gave benzyl 2-acetamido-3,6-di-O-benzyl-2-deoxy-4-O-β-D-galactopyranosyl-β-D-glucopyranoside (8). The trimethylsilyl (Me3Si) derivative of 8, on treatment with pyridineacetic anhydride-acetic acid for 2 days, gave the disaccharide derivative having an O-acetyl group selectively introduced at the primary position and Me3Si groups at the secondary positions. The latter groups were readily cleaved by treatment with aqueous acetic acid in methanol to afford benzyl 2-acetamido-4-O-(6-O-acetyl-β-D-galactopyranosyl)-3,6-di-O-benzyl-2-deoxy-β-D-glucopyranoside, which on isopropylidenation gave the desired, key intermediate benzyl 2-acetamido-4-O-(6-O-acetyl-3,4-O-isopropylidene-β-D-galactopyranosyl)-3,6-di-O-benzyl-2-deoxy-β-D-glucopyranoside (12). Reaction of 12 with 2,3,4-tri-O-benzyl-α-L-fucopyranosyl bromide under catalysis by bromide ion afforded the trisaccharlde derivative from which the title trisaccharide was obtained by systematic removal of the protective groups. The structures of the final trisaccharide and of various intermediates were established by 1H and 13C NMR spectroscopy. 相似文献
6.
Abstract Reactions of 2′,3′,4′,2″,6″-penta-O-acetyl-tetra-N-tert-butyloxycarbonyl-kanamycin-A-4″-brosylate (4b) or-4″-triflate (4c) with acetate, thiolacetate, azide, and fluoride, respectively, result in the formation of the corresponding derivatives of 4″-epi-kanamycin A (5a-d). While 4b invariably forms an elimination byproduct (9), the only side—reaction of 4c consists in a neighboring group attack with formation of a 3″-epi-4″-cyclic urethane (7). Removal of the protecting groups yields 4″-epi-(6a), 4″-thio-4″-epi-(6b), 4″-deoxy-4″-fluoro-4″-epi-(6d), 4″-azido-4″-deoxy-4″-epi-(6c), and after hydrogenation of the latter, 4″-amino-4″-deoxy-4″-epi-kanamycin A (6f). Methyl 2,6-di-O-acetyl-3-amino-3-N-tert-butyloxycarbonyl-3-deoxy-4-O-triflyl-β-D-glucopyranoside (1b) served as a model to anticipate preparation, handling, and reactivity of 4c. 相似文献
7.
Sylvie Pochet Patrice Allard Tam Huynh-dinh J. Igolen 《Journal of carbohydrate chemistry》2013,32(3):277-288
Abstract A scheme of asymmetric synthesis of C-glycosyl α-glycines is described. Reductive hydrolysis of 2-deoxy-3,5-di-O-p-toluoyl-β D-erythropentofuranose 1-cyanide (4) in the presence of N,N-diphenylethylenediamine gave the imidazolidine 5, which was converted to 2,5-anhydro-3-deoxy-4,6-di-O-p-toluoyl-β-D-allose (3)by acid hydrolysis. The aldehyde (3), chiralamine, benzoic acid and t-butyl isocyanide four component condensation afforded in good yield two diastereomeric adducts (6a and 6b), which were separated by column chromatography and deblocked to furnish 2-deoxy-β-D-erythropentofuranosyl R and S-glycines (1a) and (1b). 相似文献
8.
Pavol Kováč Herman J. C. Yeh Grace L. Jung Cornelis P. J. Glaudemans 《Journal of carbohydrate chemistry》2013,32(3):497-512
Methyl 3-O-benzyl-4, 6-O-benzylidene-α-D-mannopyranoside (2), when treated in diglyme at 1000[ddot] with DAST, undergoes a rapid reaction involving the participation of the axial methoxyl group at C-1 to give 3-O-benzyl-4, 6-O-benzylidene-2-O-methyl-α- (4) and β-D-gluco-pyranosyl fluoride (3), isolated in a combined yield of 75-80%. In the presence of pyricfine and at room temperature, the major product formed is methyl 3-O-benzyl-4, 6-O-benzylidene-2-deoxy-α-D-eiythro-hex-2-enopyranoside (11). The structures 3, 4 and 11 have been confirmed by analysis of their NMR spectral data, as well as by chemical transformations into compounds of established structure. 相似文献
9.
Ronan Van Rijsbergen Marc Anteunis André De Bruyn 《Journal of carbohydrate chemistry》2013,32(2):329-333
When 1,6-anhydro-2-azido-4-O-benzoyl-2-deoxy-β-D-glucopyranose (1 (l) was treated with allyl bromide in benzene-tetrahydrofuran solution in the presence of sodium hydride, we obtained the expected reaction product, 3-O-allyl-1,6-anhydro-2-azido-4-O-benzoyl-2-deoxy-β-D-glucopyranose (2), and the rearranged compounds 1,6-anhydro-2-azido-3-O-benzoyl-2-deoxy-β-D-glucopyranose (3) and 4-O-allyl-1,6-anhydro-2-azido-3-O-benzoyl-2-deoxy-β-D-glucopyranose (4). 相似文献
10.
F. M. Soliman Kh. M. Khalil G. Abd-el-naim 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4)
Abstract The reaction of 1,2-benzo [a] phenazine-8, 9-dione 1 and/or 1,2,3-indantrione 2, with phosphonium ylides has been studied. When 1 was reacted with two molar amounts of methoxy-(3a) and/or ethoxycarbonylmethylenetriphenylphosphorane (3b), in THF, at the reflux temp, for 3 hrs, dimethyl (4a) and/or diethyl 1,2-dihydrobenzo a furo [3,2-h] phenazine-1,2-dicarboxylate (4b), along with triphenylphosphine oxide and triphenylphosphine were obtained. On the other hand, reaction of equimolar amounts of ylides 3 with the red trione 2 in THF at room temp., afforded colourless crys tals of 2′,4′-dihydroxyspiro [indan-2,3′ (2′H)-indeno [1,2-b] pyran]-1,3,5′(4′H)-trione diacetate (5a) or dipropionate (5b), together with triphenylphosphine oxide. Formation of 6-membered dihydro aromatic ring like 5, is considered as a new reaction of phos phoranes. The structure of the new compounds 4 and 5 was confirmed and the reaction mechanisms are discussed. 相似文献
11.
Donald E. Kiely Jamil W. Talhouk James M. Riordan Kathy Gray 《Journal of carbohydrate chemistry》2013,32(4):427-438
Abstract Acid hydrolysis of 6-deoxy-1,2-O-isop ropylidene-α-d-xylo-hexo-furanos-5-ulose (4) yielded gummy 6-deoxy-d-xylo-hexos-5-ulose (1) as an isomeric mixture of two furanose forms, 6-deoxy-α-d-xylo-hexo-furanos-5-ulose and 6-deoxy-β-d-xylo-hexofuranos-5-ulose, and a pyranose structure 1R, 5R-6-deoxy-d-xylo-hexopyranos-5-ulose. The combined percentage (64%) of the furanoses represents an unusually large amount of free carbonyl form for a sugar when compared to simple hexoses and 2-hexuloses. Isomeric structures were determined in deuterium oxide solution by 1H and 13C NMR. 相似文献
12.
Bromoacetylation of methyl 2,4-di-O-benzoyl-3-deoxy-3-fluoro-β-D-galactopyranoside, followed by the cleavage of the methoxy group from the resulting 6-O-bromoacetyl derivative 2 with 1,1-dichloromethyl methyl ether gave 2,4-di-0-benzoyl-6-0-bromoacetyl-3-deoxy-3-fluoro-α-D-galactopyranosyl chloride (3). Reaction of 3 with methyl 2,3,4-tri-O-benzoyl-β-D-galactopyranoside promoted by silver trifluoromethanesulfonate afforded methyl 0-(2,4-di-O-benzoyl-6-O-bromoacetyl-3-deoxy-3-fluoro-β-D-galacto-pyranosyl)-(1→6)-2,3,4-tri-O-benzoyl-β-D-galactopyranoside (5). O-Debromoacetylation of 5 with thiourea gave the disaccharide nucleophile 6 which was condensed with 2,3,4,6-tetra-O-benzoyl-α-D-galactopyranosyl bromide to afford the expected β-(trans)-linked trisaccharide derivative 7. Debenzoylation of 7 gave the methyl β-glycoside 8 of the (1→6)-linked D-galactotriose having the HO-3 of the internal residue replaced by a fluorine atom. Compound 8 was used to further delineate the subsites in the combining area of the monoclonal anti-(1→6)-β-D-galactan-specific immunoglobulin IgA J539. 相似文献
13.
Roger W. Binkley Michael G. Ambrose David G. Hehemann 《Journal of carbohydrate chemistry》2013,32(2):203-219
Abstract The reactions of bromide, chloride, and iodide ions with 1,3,4, 6-tetra-O-acetyl-2-O-(trifluoromethylsulfonyl) -α-D-glucopyranose (2) and with 1, 3, 4, 6-tetra-O-acetyl-2-O-(trifluoromethylsulfonyl)-β-D-mannopyranose (3) gave good to excellent yields of the corresponding deoxyhalogeno sugars. In contrast, when the gluco triflate 2 and tetra-butylammonium fluoride were heated under reflux in benzene, only 5-(acetoxymethyl)-2-formylfuran (13) was formed. Reaction of the manno triflate 3 under similar conditions produced 1, 3,4, 6-tetra-O-acetyl-2-deoxy-2-fluoro-β-D-gluco-pyranose (17), 1. 3, 4. 6-tetra-O-acetyl-2-deoxy-β-D-erythro-hex-2-eno-pyranose (18), 4,6-di-O-acetyl-1, 5-anhydro-2-deoxy-D-erythro-hex-l-enitol-3-ulose (19), and 1, 2, 3, 4, 6-penta-O-acetyl-β-D-glucopyranose (20). The mechanisms of the reactions of The triflates 2 and 3 with fluoride ion are discussed. 相似文献
14.
6-Alkylpyrano [3,2-c] quinolin-5(2H)-ones(11a-e) were obtained in excellent yields by simply refluxing propynyl and butymyl ethers (6) of 4-hydroxy-1-alkylquinolin-2H-ones (2) in chlorobenzene for 10h, 5-Prop-2-ynyloxy-2H-pyrano [3,2-c] quinoline (12) was also obtained from the thermal rearrangement of 2,4-bis prop-2-ynyloxyquinoline (4). 相似文献
15.
Ana Calvo-mateo María-José Camarasa Angel Díaz-Ortíz Federico G. De las Heras Antonio Alemany 《Journal of carbohydrate chemistry》2013,32(3):395-404
Abstract Aldol reaction of 1,2-O-isopropylidene-5-O-tertbutyl-dimethylsilyl-α-D-erythro-pentofuranos-3-ulose (1) with acetone in the presence of aqueous K2CO3 afforded 3-C-acetonyl-1,2-O-isopropylidene-5-O-tertbutyl-dimethylsilyl-α-D-ribofuranose(2). Similar reaction of 1,2:5, 6-di-o-isopropylidene- α-D-ribo-hexofuranos-3-ulose (3) afforded 3-C-acetonyl-1,2:5, 6-di-o-isopropylidene- α-D-allofuranose (4) and (1R, 3R, 7R, 8S, 10R)-perhydro-8-hydroxy-5,5,10-trimethyl-2,4,6,11,14-pentaoxatetracyclo[8,3,1,01,8,03,7] tetradecane. The stereochemistry of the new chiral centers were determined by 1H NOE experiments. 相似文献
16.
Abstract Methyl 6-deoxy-6-fluoro-β-d-galactopyranoside has been obtained by treatment of methyl β-d-galactopyranoside with diethyl-aminosulfur trifluoride (DAST). Improvements over the existing syntheses of methyl 2, 3-di-O-benzyl-4-deoxy-4-fluoro-β-d-galacto-pyranoside from the corresponding 6-O-substituted 4-O-arylsul-fonyl-d-gluco derivatives are described. 13C NMR spectra of a series of methyl deoxyfluoro-β-d-galactopyranosides and their per-O-acetyl derivatives have been measured. The data obtained can be used as an aid for the interpretation of 13C NMR spectra of deoxyfluoro-β-d-galactopyranose-containing oligosaccharides and related substances. 相似文献
17.
Abstract Starting from the kanamycin A 4″,6″-ditriflate 6 und -6″-brosy-late-4″-triflate 8, respectively, the following derivatives were prepared: 4″,6″-dideoxy-4″,6″-difluoro-4″-epi- (20), 4″,6″-dideoxy-4″-fluoro-4″-epi- (22), 6″-deoxy-6″-fluoro-4″-epi- (19), and 6″-deoxy-4″-epi-kanamycin A (21). C NMR and antibacterial data are given. 相似文献
18.
Abstract Regioselective cleavage of 1,6-anhydro-maltose (1) with periodate and the subsequent recyclization with nitromethane gave 1,6-anhydro-3′-deoxy-3′-nitro-disaccharides (3). Three diastereomers, prepared by benzylidenation of 3, were separated by column chromatography. Each of 4′,6′-O-benzylidene derivatives successively underwent debenzylidenation, reduction of the nitro group, and peracetylation to give 3′-acetamido-3′-deoxy-disaccharide derivatives (7, 8, and 9). The configurations of the 3-amino sugar moietres in 7 (D-gluco), 8 (D-manno) and 9 (D-galacto) were determined on the basis of the 1H NMR data. The main product (7) was further modified to the 6-deoxy-6-nitro derivative. 相似文献
19.
Abstract 2-Deoxy-d-arabino-hexose (1), 2-acetamido-2-deoxy-d-glucose (2), and 2-deoxy-2-trifluoroacetamido-d-glucose (3) were each treated with 1,1-dimethoxycyclohexane or 1,1-dibenzyloxycyclohexane in 1,4-dioxane in the presence of p-toluenesulfonic acid. The major products were the 1,1-dimethyl or 1,1-dibenzyl acetals (4-9) of 3,4:5,6-di-O-cyclohexylidene-2-deoxy-aldehydo-d-arabino-hexose, and of 2- (acylamino)-3,4:5,6-di-O-cyclohexylidene-2-deoxy-aldehydo-D-glucose. The dibenzyl acetal derivatives were converted, by hydro-genolysis, into the corresponding, acyclic aldehydes (10-12) in good yields. 相似文献
20.
Tsutomu Tsuchiya Yoshiaki Takahashi Makoto Endo Sumio Umezawa Hamao Umezawa 《Journal of carbohydrate chemistry》2013,32(4):587-611
2′,3′-Dideoxy-2′-fluorokanamycin A (23) was prepared by condensation of 6-azido-4-0-benzoyl-2,3,6-trideoxy-2-fluoro-α-D-ribo-hexopyranosyl bromide (13) and a protected disaccharide (19). Methyl 4,6-0-benzylidene-3-deoxy-β-D-arabino-hexopyranoside (5) prepared from methyl 4,6-0-benzylidene-3-chloro-3-deoxy-β-D-allo-hexopyranoside (1) by oxidation with pyridinium chlorochromate followed by reduction with Na2 S2O4 was fluorinated with the DAST reagent to give methyl 4,6-O-benzylidene-2,3-dideoxy-2-fluoro-β-D-ribo-hexopyranoside (7). Successive treatment of 7 with NBS, NaN3 and SOBr2 gave 13. The structure of the final product (23) was determined by the 1H and 19F and shift-correlated 2D NMR spectra. 相似文献