- Synthesis of N-Glycosides.Formation of Glucosylamine by Reaction of 2,3,4,6-Tetra-O-benzyl-D-glucopyranose with Acetonitrile in the Presence of Trifluoromethanesulfonic Anhydride
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The synthesis of glucosylamine by reaction of 2,3,4,6-tetra-O-benzyl-D-glucopyranose with acetonitrile in the presence of trifluoromethanesulfonic anhydride was shown to proceed through an intermediate oxazoline.
- Pavia, Andre A.,Ung-Chhun, Sak N.,Durand, Jean-L.
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Read Online
- A dehydrative glycosylation protocol mediated by nonafluorobutanesulfonyl fluoride (NfF)
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A new dehydrative glycosylation protocol that proceeds through selective activation of glycosyl hemiacetals with nonafluorobutanesulfonyl fluoride (NfF) has been disclosed. Contrary to the major classical glycosylation reactions that proceed under acidic
- Reddy, D. Prabhakar,Tang, Yu,Yu, Biao
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- Dehydrative Glycosylation Enabled by a Comproportionation Reaction of 2-Aryl-1,3-dithiane 1-Oxide?
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A new dehydrative glycosylation reaction has been established by capitalizing on the comproportionation reaction of 2-aryl-1,3-dithiane 1-oxides promoted by triflic anhydride (Tf2O). By wedding the high potency of thiophilic promoter system with the step efficiency of dehydrative glycosylation, this reagent underwent facile intermolecular oxothio acetalization with C1-hemiacetal donor to install a temporary leaving group, rendering a transient electrophilic center at the remote site to the anomeric position. The sulfenyl triflate tethered at the terminus concomitantly activated the sulfide intramolecularly to afford the oxocarbenium ion, thereby facilitating the title glycosylation. Aside from accommodating broad range functional groups and inactive hemiacetal substrates, the present activation protocol also proved expedient for 1,3-diol protection. Most importantly, this method further provided a fresh perspective for the application of sulfur chemistry to carbohydrate chemistry.
- Cai, Lei,Zeng, Jing,Li, Ting,Xiao, Ying,Ma, Xiang,Xiao, Xiong,Zhang, Qin,Meng, Lingkui,Wan, Qian
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supporting information
p. 43 - 49
(2019/11/28)
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- 2-Allylphenyl glycosides as glycosyl donors for sugar coupling
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Glycosylations employing 2-allylphenyl glycoside, a new type of stable glycosyl donor, were optimized and explored with a variety of acceptors promoted by ICl/AgOTf. The utility of the protocol was further demonstrated with an efficient synthesis of the disaccharide fragment of bleomycins.
- Luo, Shun-Yuan,Tripathi, Ashish,Zulueta, Medel Manuel L.,Hung, Shang-Cheng
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p. 197 - 201
(2012/06/30)
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- Formation of O-glycosidic linkages from 1-hydroxy sugars by bismuth(III) triflate-catalyzed dehydrative glycosidation
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This paper describes the direct formation of various O-glycosidic linkages from 1-hydroxy sugars by bismuth(III) triflate-catalyzed dehydrative glycosidation. The condensation reactions of 1 -hydroxy sugars with some primary alcohols in the presence of on
- Yamanoi, Takashi,Inoue, Ryo,Matsuda, Sho,Iwao, Kazuya,Oda, Yoshiki,Yoshida, Akihiro,Hamasaki, Keita
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experimental part
p. 445 - 460
(2009/09/30)
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- 2-Allyloxyphenyl glycoside as a new and stable type of glycosyl donors
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A high-yielding coupling of a new and stable type of glycosyl donors, namely 2-allyloxyphenyl glycoside, with a variety of alcohols via NIS/TfOH reagent combination as effective activators at room temperature is described here.
- Lee, Jinq-Chyi,Pan, Guan-Rong,Kulkarni, Suvarn S.,Luo, Shun-Yuan,Liao, Chun-Chen,Hung, Shang-Cheng
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p. 1621 - 1624
(2007/10/03)
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- Sulfoxide Covalent Catalysis: Application to Glycosidic Bond Formation
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A versatile glycosylation reaction is used to establish the process of sulfoxide covalent catalysis. Hemiacetals are activated by benzenesulfonic anhydride and a dialkyl sulfoxide catalyst, nBu2SO, for coupling with various nucleophiles (Nu; se
- Boebel, Timothy A.,Gin, David Y.
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p. 5874 - 5877
(2007/10/03)
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- Synthesis of methyl O-α-D-mannosyl-(1→4)-[(3-O-methyl-α-D-mannosyl) -(1→4)-]n3-O-methyl-α-D-mannosides (n = 0, 1, and 2) via dehydrative glycosylation
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Methyl O-α-D-mannopyranosyl-(1→4)-[(3-O-methyl-α-D-mannopyranosyl -(1→4)-]n3-O-methyl-α-D-mannopyra-nosides (n = 0, 1, and 2), the lowest homologs related to the 3-O-methylmannose polysaccharides (MMP) from Mycobacterium smegmatis, were synthesized via dehydrative glycosylation reactions. The reagent systems, composed of p-nitrobenzenesulfonyl chloride, silver trifluoromethanesulfonate, and triethylamine, of p-nitrobenzenesulfonyl chloride, silver trifluoromethanesulfonate, and 1, 8-diazabicyclo[5.4.0]undec-7-ene, and of trimethylsilyl trifuloromethanesulfonate and pyridine were useful.
- Hirooka, Motoko,Terayama, Megumi,Mitani, Emi,Koto, Shinkiti,Miura, Asako,Chiba, Kayo,Takabatake, Ayano,Tashiro, Takako
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p. 1301 - 1309
(2007/10/03)
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- A new, efficient glycosylation method for oligosaccharide synthesis under neutral conditions: Preparation and use of new DISAL donors
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Efficient, stereoselective glycosylation methods are required for the synthesis of complex oligosaccharides as tools in glycobiology. All glycosylation methods, which have found wide acceptance, rely on Lewis acid activation of glycosyl donors prior to glycosylation. Here, we present a new and efficient method for glycosylation under neutral or mildly basic conditions. Glycosides of methyl 2-hydroxy-3,5-dinitrobenzoate (DISAL) and its para regioisomer, methyl 4-hydroxy-3,5-dinitrobenzoate, were prepared by nucleophilic aromatic substitution. In a first demonstration of their potential as glycosyl donors, stereospecific glycosylation of methanol was achieved. In the glycosylation of more hindered alcohols, the β-donor proved more reactive, and α-glucosides were predominantly formed. Glycosylation of protected monosaccharides, with free 6-0H or 3-OH, proceeded smoothly in 1-methyl-2-pyrrolidinone (NMP) at 40-60 °C in the absence of Lewis acids and bases in good to excellent yields. Glycosylation of 3-OH gave the α-linked disaccharide only.
- Petersen,Jensen
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p. 6268 - 6275
(2007/10/03)
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- Rational design and synthesis of a 1,1-linked disaccharide that is 5 times as active as sialyl Lewis X in binding to E-selectin
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We describe here a rational design and synthesis of (3-O-carboxymethyl)-β-D-galactopyranosyl α-D-mannopyranoside which is 5 times as active as sialyl Lewis X in binding to E-selectin and also effective against P- and L-selectin. A new method for the 1,1-g
- Hiruma, Kazumi,Kajimoto, Tetsuya,Weitz-Schmidt, Gabriel,Ollmann, Ian,Wong, Chi-Huey
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p. 9265 - 9270
(2007/10/03)
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- Molecular sieves promote stereocontrolled αα-disaccharide formation via direct dimerization of free sugars
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Some commercial molecular sieves promote direct dimerization of free pyranose and furanose sugars stereoselectively into the corresponding α,α-disaccharides.
- Posner, Gary H.,Bull, D. Scott
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p. 6279 - 6282
(2007/10/03)
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- The Use of O-Glycosyl Trichloroacetimidates in The Synthesis of Unsymmetrical Trehalose Analogues
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The coupling of O-glycosyl trichloroacetimidates with 2,3,4,6-tetra-O-benzylated monosaccharides (gluco, manno, galacto) promoted by TMSOTf is described, and the compositions of the crude reaction mixtures, determined by 13C NMR spectroscopy, are presente
- Ronnow, Tor E. C. L.,Meldal, Morten,Bock, Klaus
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p. 2109 - 2122
(2007/10/02)
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- TMS triflate induced synthesis of 1,1'-disaccharides from 1-hydroxy sugars
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A variety of 1,1'-disaccharides have been prepared by TMS triflate induced coupling of 1-hydroxy sugars in reasonable yield.
- Nishizawa,Garcia,Noguchi,Komatsu,Hatakeyama,Yamada
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p. 2400 - 2402
(2007/10/02)
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- Synthesis and glycosylation shift of 1,1'-disaccharides
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Nineteen kinds of nonreducing 1,1'-disaccharides have synthesized by modified Koenigs-Knorr method, and characterized by NMR. The glycosylation shift of each anomeric carbon has been estimated.
- Nishizawa,Kodama,Yamane,Kayano,Hatakeyama,Yamada
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p. 982 - 984
(2007/10/02)
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- THE HIGHLY STEREOSELECTIVE SYNTHESIS OF PERBENZYLATED α,α-TREHALOSE AND ITS D-GALACTO AND D-MANNO ANALOGS
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Treatment of 2,3,4,6-tetra-O-benzyl-1-O-trimethylsilyl-α,β-D-glucopyranose in dichloromethane with trimethylsilyl triflate catalyst gave the corresponding α,α- and α,β-trehaloses in quantitative yield.A similar treatment of D-galacto and D-manno analogs gave exclusively the corresponding α,α-anomers, respectively.
- Yoshimura, Juji,Hara, Kazutoshi,Sato, Tatsuya,Hashimoto, Hironobu
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p. 319 - 320
(2007/10/02)
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- Stereoselective α-Glucosylation with Tetra-O-benzyl-α-D-glucose and a Mixture of Trimethylsilyl Bromide, Cobalt(II) Bromide, Tetrabutylammonium Bromide, and a Molecular Sieve. A Synthesis of 3,6-Di-O-(α-D-glucopyranosyl)-D-glucose
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A mixture of trimethylsilyl bromide, cobalt(II) bromide, tetrabutylammonium bromide, and a molecular sieve (4A) is effective for the stereoselective, one-stage α-glucosylation of alcohol with 2,3,4,6-tetra-O-benzyl-α-D-glucopyranose in dichloromethane.Using this procedure, several disaccharide derivatives as well as O-α-D-glucopyranosyl-(1 -> 3)-O- 6)>-D-glucopyranose are synthesized.
- Koto, Shinkiti,Morishima, Naohiko,Kusuhara, Chiharu,Sekido, Shigeko,Yoshida, Toyosaku,Zen, Shonosuke
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p. 2995 - 2999
(2007/10/02)
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- NOUVELLE METHODE DE SYNTHESE STEREOSELECTIVE DE GLYCOSIDES. SYNTHESE DES α,α-TREHALOSE, ANALOGUES galacto, manno ET AUTRES α-D-GLYCOSIDES
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In the presence of trifluoromethanesulfonic (triflic) anhydride as catalyst and dichloromethane as solvent, in the cold, 2,3,4,6-tetra-O-benzyl-D-glucopyranose, 2,3,4,6-tetra-O-benzyl-D-galactopyranose, and 2,3,4,6-tetra-O-benzyl-D-mannopyranose were converted in almost quantitative yield to a 2:1 mixture of the corresponding α,α-(1->1) and α,β-(1->1) disaccharides.Hence, pure 2,3,4,6,2',3',4',6'-octa-O-benzyl derivatives of α,α-trehalose, and the D-galacto and D-manno analogues were obtained, after column chromatography, in 55-65 percent yield.Hydrogenolysis gave the corresponding free sugars.The pure anomers were obtained in 10-34 percent yield.The potentiality of the method was demonstrated by the synthesis of 2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl 2,3:4,5-di-O-isopropylidene-β-D-fructopyranoside in 50 percent yield, and of N-(benzyloxycarbonyl)-3-O-(2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl)-L-threonine methyl ester in 65 percent yield.
- Pavia, Andre A.,Rocheville, Jean-Michel,Ung, Sak N.
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- The Glucosylation of Several Alcohols with Tetra-O-benzyl-α-D-glucopyrmnose and a Mixture of p-Nitrobenzenesulfonyl Chloride, Silver Trifluoromethanesulfonate, and Triethylamine
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A novel glucosylation of several alcohols using 2,3,4,6-tetra-O-benzyl-α-D-glucopyranose and a ternary mixture of p-nitrobenzenesulfonyl chloride, silver trifluoromethanesulfonate, and triethylamine is presented.
- Koto, Shinkiti,Sato, Tadaaki,Morishima, Naohiko,Zen, Shonosuke
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p. 1761 - 1762
(2007/10/02)
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