Synthesis of L-fucose

Dejter-Juszynski, Marta; Flowers, Harold M.

doi:10.1016/s0008-6215(00)82872-4

Cited by 24 publications

(16 citation statements)

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“…Synthesis of versatile GDP-l-fucose analogues from d-galactose: Because synthetic studies on GDP-l-fucose analogues had revealed a tolerance at the C6 position for FucTs-catalyzed glycosylations, [30,37,38] we selected compound 1 as an ideal fluorogenic donor (naphthylmethyl) substrate for use with acceptor substrate 2 (dansyl) as shown in Scheme 1. We established an efficient synthetic route to a novel fluorescence-labeled GDP-l-fucose derivative 1 via a key (10), by using d-galactose as a starting material.…”

Section: Resultsmentioning

confidence: 99%

“…6-O-tert-Butyldimethylsilyl-2,3:4,5-di-O-isopropylidene-d-galactose dimethyl dithioacetal (5): Compound 5 was synthesized from compound 4 [37] according to a previously reported procedure, [43] and the details are described in the Supporting Information.…”

Section: Synthesis Of Novel Gdp-fucose Derivativesmentioning

confidence: 99%

“…[30,38] Conversion of the d-galacto into the l-galacto configuration was carried out by chemical modifications of compound 5, which is derived from a known d-galactose diethyl dithioacetal 4, [37] as shown in Scheme 2. Selective liberation of the thioacetal 5 yielded an alcohol 6, which was tosylated and subjected to a subsequent substitution reaction to afford the fully protected azide 8 in high yield.…”

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confidence: 99%

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FRET‐Based Direct and Continuous Monitoring of Human Fucosyltransferases Activity: An Efficient synthesis of Versatile GDP‐L‐Fucose Derivatives from Abundant d‐Galactose

Maeda

Nishimura

2007

Chemistry A European J

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We have developed a facile and versatile protocol for the continuous monitoring of human fucosyltransferases activity by using fluorescence energy resonance transfer (FRET), and have explored the feasibility of its use in an inhibitor screening assay. A convenient sugar nucleotide with a fluorogenic probe, 6-deoxy-6-N-(2-naphalene-2-yl-acetamide)-beta-L-galactopyranos-1-yl-guanosine 5'-diphosphate disodium salt (1), was efficiently synthesized from naturally abundant D-galactopyranose via a key intermediate, 6-azide-1,2,3,4-tetra-O-benzoyl-6-deoxy-beta-L-galactopyranose (10). It was demonstrated that the combined use of the glycosyl donor 1 and a dansylated acceptor substrate, sialyl-alpha2,3-LacNAc derivative (2) allowed us to carry out highly sensitive, direct, and continuous in vitro monitoring of the generation of sialyl Lewis X (SLe x), which is catalyzed by human alpha-1,3-fucosyltransferase VI (FUT-VI). A kinetic analysis revealed that compound 1 was an excellent donor substrate (KM=0.94 microM and Vmax=0.14 microM min(-1)) for detecting human FUT-VI activity. To the best of our knowledge, this synthetic fluorogenic probe is the most sensitive and selective donor substrate for FUT-VI among all of the known GDP-Fuc analogues, including the parent GDP-Fuc. When a dansylated asparagine-linked glycopeptide 20, which is derived from egg yolk was employed as an alternate acceptor substrate, a FRET-based assay with compound 1 could be used to directly monitor the alpha1,6-fucosylation at the reducing terminal GlcNAc residue by human FUT-VIII (KM=175 microM and Vmax=0.06 microM/ min); this indicates that the present method might become a general protocol for the characterization of various mammalian fucosyltransferases in the presence of designated fluorogenic acceptor substrates. The present protocol revealed that compound 23, which was obtained by a 1,3-dipolar cycloaddition between the disodium salt 16 and 1-ethynyl-naphthalene exhibits highly potent inhibitory effects against the FUT-VI-mediated sialyl Lewis X synthesis (IC50=5.4 microM).

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Section: Resultsmentioning

confidence: 99%

Section: Synthesis Of Novel Gdp-fucose Derivativesmentioning

confidence: 99%

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FRET‐Based Direct and Continuous Monitoring of Human Fucosyltransferases Activity: An Efficient synthesis of Versatile GDP‐L‐Fucose Derivatives from Abundant d‐Galactose

Maeda

Nishimura

2007

Chemistry A European J

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“…[ 121 (100 g, 0.32 mol) according to [15]. FC (AcOEt/hexane 1 :1, AcOEt) and recrystallization in acetone/Et20 gave 20 in 78% yield.…”

Section: Benzyl 2-acetamido-34-di-o-acetyl-2-deoxy-a -D-glucopyranosmentioning

confidence: 99%

Analogues of Sialic Acids as Potential Sialidase Inhibitors. Synthesis of C₆ and C₇ Analogues of N‐Acetyl‐6‐amino‐2,6‐dideoxyneuraminic Acid

Glänzer

Györgydeák

Bernet

et al. 1991

Helvetica Chimica Acta

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The piperidines 12-18, piperidinose analogues of NeuSAc (1) with a shortened side chain, were synthesized from N-acetyl-o-glucosamine via the azidoalkene 32 and tested as inhibitors of Vibrio cholerae sialidase. Deoxygenation at C(4) of the uronate 22, obtained from the known D-GIcNAc derivative 20, was effected by 8-elimination (+23), exchange of the AcO at C(3) with a (t-Bu)Me,SiO group and hydrogenation (-26; Scheme 1 ) . Chain extension of 26 by reaction with Me3SiCH2MgCI gave the o-ido-dihydroxysilane 28, which was transformed into the unsaturated L-xylo-mesylate 29 and further into the L-lyxo-alcohol30, the mesylate 31, and the L-xylo-azide 32. The derivatives 29-31 prefer a sickle zig-zag and 32 mainly an extended zig-zag conformation (Fig. 2). The piperidinecarboxylate 15 was obtained from 32 by ozonolysis (+ 33), intramolecular reductive amination (+ 34), and deprotection, while reductive amination of 34 with glycolaldehyde (+ 35) and deprotection gave 16 (Scheme 2). An intramolecular azide-olefin cycloaddition of 32 yielded exclusively the fused dihydrotriazole 36, while the lactone 39 did not cyclize (Scheme 3). Treatment of 36 with AcOH (-37) followed by hydrolysis (-38) and deprotection led to the amino acid 18. To prepare the (hydroxymetby1)piperidinecarboxylates 12 and 17, 32 was first dihydroxylated (Scheme 4). The L-gluco-diol40 was obtained as the major product, in agreement with Kishi's rule. Silylation of 40 (+ 42), oxidation with periodinane (+ 44), and reductive amination gave the L-gluco-piperidine 45. It was, on the one hand, deprotected to the amino acid 12 and, on the other hand, N-phenylated (+46) and deprotected to 17. While 45 and 12 adopt a ,C5 conformation, the analogous N-Ph derivatives 46 and 17 adopt a 5C2 and a B3,6 conformation, respectively, on account of the allylic 1,3-strain. The conformational effects of this 1,3-strain are also evident in the carbamate 47, obtained from 45 (Scheme 5), and in the C(2)-epimerized bicyclic ether 48, which was formed upon treatment of 47 with (diethy1amino)sulfur trifluoride (DAST). Fluorination of 40 with DAST (-49) followed by treatment with AcOH led to the o-ido-fluorohydrin 50. Oxidation of 50 (-51) followed by a Staudinger reaction and reduction with NaBH3CN afforded the (fluoromethy1)piperidine 52, while reductive amination of 51 with H,/Pd led to the methylpiperidine 55, which was similarly obtained from the keto tosylate 54 and from the dihydrotriazole 36. Deprotection of 52 and 55 gave the amino acids 13 and 14, respectively. The aniline 17 does not inhibit V. cholerae sialidase; the piperidines 12-16 and 18 are weak inhibitors, evidencing the importance of an intact 1,2,3-trihydroxypropyl side chain.Introduction. -Several piperidine [ 11 and pyrrolidine [2] analogues of N-acetylneuraminic acid (NeuSAc, 1) are inhibitors of Vibrio cholerae neuraminidase. As shown in Fig. I , the analogue 2 is the most active inhibitor, its epimer 3 is somewhat weaker, and the epimer 4, possessing an axial COOH group, is not an inhibitor. The dependen...

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“…Of particular relevancv in this connection was the discovery by Lemieux and co-workers (4), that stable a-glycosyl halides anomerize by halide ion catalysis to give their more highly reactive Panomers, albeit in low concentration, a phenomenon which can be utilized in a-glycoside synthesis (5-7). It was found, furthermore, that certain specific groups present in positions other than C-2 may influence reaction rates and have a directive effect which can be enlisted for making 1,2-cis glycosides (5,(8)(9)(10)(11)(12)(13)(14), and such glycosides have also been obtained from reactive glycosyl derivatives possessing an electropositive leaving group (15). Nevertheless, the scope of some of the& approaches is still uncertain and a lack of predictability exists.…”

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confidence: 99%

Concerning the Problem of Stereospecific Glycosylation. Synthesis and Methanolysis of some 2-O-Benzylated D-Galactopyranosyl and D-Galactofuranosyl Halides

Fréchet¹,

Baer²

1975

Can. J. Chem.

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. Can. J. Chem. 53,670(1975). Acetolysis of 1,6-anhydro-2,3,4-tri-O-benzyl-~-~-galactopyranose (3) followed by de-0-acetylation and p-nitrobenzoylation gave 2,3,4-tri-O-benzy1-1,6-di-O-p-nitrobenzoyl-~-~-galactopyranose (4) which was converted into 2,3,4-tri-0-benzyl-6-0-p-nitrobenzoyl-a-Dgalactopyranosyl bromide (5). Benzylation of methyl 4,6-0-benzylidene-a-D-galactopyranoside (6) gave the 2,3-dibenzyl ether (7) which was hydrolyzed to 2,3-di-0-benzyl-D-galactose (8). p-Nitrobenzoylation of 8 furnished 2,3-di-O-benzyl-l,5,6-tri-O-p-nitrobenzoyl-(3-~-galactofuranose (9) and an isomer, presumably a (3-pyranose derivative (10). Compound 9 was converted into 2,3-di-0-benzyl-5,6-di-O-p-nitrobenzoyl--~-galactofuranosyl bromide (11) and chloride (12). The new halides 5, 11, and 12 as well as known 2,3,4,6-tetra-0-benzyl-a-Dgalactopyranosyl bromide (1) and chloride (2) were subjected to methanolysis in dichloromethane solution in the presence of methanol alone and in the presence of tetrabutylammonium bromide, mercuric cyanide, and silver tetrafluoroborate, respectively, and the ratios of anomeric glycosides produced were examined by n.m.r. soectroscoov. Factors influencing stereoselectivity %these reactions are discussed. The new methil a-and (3:glycosides derived fcom 5 (13 a n d 14) and the methyl a-glycoside (15) produced from 11 and 12 were isolated, and methyl 2,3,5.6-tetra-0-benzyl-a-D-galactofuranoside (16) was prepared for the first time.

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Synthesis of L-fucose

Cited by 24 publications

References 3 publications

FRET‐Based Direct and Continuous Monitoring of Human Fucosyltransferases Activity: An Efficient synthesis of Versatile GDP‐L‐Fucose Derivatives from Abundant d‐Galactose

FRET‐Based Direct and Continuous Monitoring of Human Fucosyltransferases Activity: An Efficient synthesis of Versatile GDP‐L‐Fucose Derivatives from Abundant d‐Galactose

Analogues of Sialic Acids as Potential Sialidase Inhibitors. Synthesis of C₆ and C₇ Analogues of N‐Acetyl‐6‐amino‐2,6‐dideoxyneuraminic Acid

Concerning the Problem of Stereospecific Glycosylation. Synthesis and Methanolysis of some 2-O-Benzylated D-Galactopyranosyl and D-Galactofuranosyl Halides

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Synthesis of L-fucose

Cited by 24 publications

References 3 publications

FRET‐Based Direct and Continuous Monitoring of Human Fucosyltransferases Activity: An Efficient synthesis of Versatile GDP‐L‐Fucose Derivatives from Abundant d‐Galactose

FRET‐Based Direct and Continuous Monitoring of Human Fucosyltransferases Activity: An Efficient synthesis of Versatile GDP‐L‐Fucose Derivatives from Abundant d‐Galactose

Analogues of Sialic Acids as Potential Sialidase Inhibitors. Synthesis of C6 and C7 Analogues of N‐Acetyl‐6‐amino‐2,6‐dideoxyneuraminic Acid

Concerning the Problem of Stereospecific Glycosylation. Synthesis and Methanolysis of some 2-O-Benzylated D-Galactopyranosyl and D-Galactofuranosyl Halides

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Analogues of Sialic Acids as Potential Sialidase Inhibitors. Synthesis of C₆ and C₇ Analogues of N‐Acetyl‐6‐amino‐2,6‐dideoxyneuraminic Acid