Preparation of pyranoid glycal derivatives from phenyl thioglycosides and glycosyl phenyl sulphones

Fernández‐Mayoralas, Alfonso; Marra, Alberto; Trumtel, Michel; Veyrières, Alain; Sînaÿ, Pierre

doi:10.1016/0008-6215(89)84061-3

Cited by 83 publications

(29 citation statements)

References 36 publications

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“…The galacto configuration of the resulting 2-azido-2-deoxyselenoglycosides was confirmed by 'H NMR spectroscopy. For 96, 9c, 9d, and 9e, the values of coupling constants of H2 with HI (==5 Hz indicating a cis relationship) and with H3 (6-7 Hz) were in agreement with values already reported for such 3,4-0-isopropylidene galacto derivatives (20). For 106 and 10c the corresponding coupling constants (J,,, = 5.2 Hz and J2,3 = 10.5 Hz) clearly indicated the a-d-galacto configuration.…”

Section: Resultssupporting

confidence: 89%

Preparation of diversely protected 2-azido-2-deoxyglycopyranoses from glycals

Czernecki¹,

Ayadi²

1995

Can. J. Chem.

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A new and efficient preparation of diversely protected 2-azido-2-deoxyglycopyranosides from the corresponding glycals is described. The glycals are first transformed into protected phenyl 2-azido-2-deoxyselenoglycopyranosides by azido-phenylselenylation. Two procedures were employed according to the protecting groups present: sodium azide and diphenyldiselenide in the presence of (diacetoxyiodo)benzene for peracetylated glycals (Procedure A) or trimethylsilyl azide and tetra-n-butylammonium fluoride in the presence of N-phenylselenophthalimide for perbenzylated glycals (Procedure B). A gluco-manno mixture (90%) is obtained from protected d-glucal whereas only the galacto isomer is formed from protected d-galactal(75%). The compatibility of the second procedure with one free hydroxyl group and a variety of protecting groups was verified with 1,5-anhydro-2-deoxy-3,4-O-isopropylidene-d-lyxo-hex-l -enitol and its 6-0-acety I, 6-0-allyl, 6-0-benzyl, and 6-0-tert-butyldimethylsilyl derivatives as well as with 1,s-anhydro-4,6-0-benzylidene-2-deoxy-d-lyxohex-1-enitol and its 3-0-acetyl and 3-0-benzyl derivatives, which were transformed into phenyl2-azido-2-deoxy-a-d-selenogalactopyranoside derivatives in good yield. In the second step, hydrolysis of these selenoglycosi&s afforded diversely protected glycopyranoses in high yield. Peracetylated derivatives were hydrolyzed in the presence of N-iodosuccinimide, whereas mercury trifluoroacetate was employed for 3,4-0-isopropylidene, 4,6-0-benzylidene, and perbenzylated derivatives. In some cases the two steps can be canied out without isolation of the intermediate selenoglycoside.Key words: glycals, 2-azido-2-deoxygalactopyranose, 2-azido-2-deoxyglucopyranose, selenoglycosides.RCsumC : On dCcrit une nouvelle prCparation efficace de divers 2-azido-2-dCsoxyglycopyranosides protCgCs de diverses manikres 8 partir des glycals correspondants. Dans la premikre Ctape, on transforme les glycals en 2-azido-2-dCsoxysCICnoglycopyranosides de phenyle protCgCs par azidophCnylsClCnylation. On a utilisC deux mCthodes suivant la nature des groupes protecteurs presents : azoture de sodium et diphCnyldisClCnure en prCsence de (diac6toxyiodo)benzkne avec les glycals peracCtylCs (rnCthode A) ou azoture de trimCthylsilyle et fluorure de tCtra-n-butylammonium en prCsence de N-phCnylsC1Cnophtalimide avec les glycals perbenzylCs (mCthode B). On obtient un mClange gluco-manno (90%) 8 partir du d-glucal alors que l'on obtient uniquement l'isornkre galacto 8 partir du d-galactal(75%). Utilisant le 1,5-anhydro-2-dCsoxy-3,4-O-isopropylidkne-d-lyxohex-1-Cnitol et ses dCrivCs ainsi que le 1,sanhydro-4,6-O-benzylidkne-2-dCsoxy-d-lyo-hex-l-Cnitol et ses derives 3-0-acCtyl-et 3-0-benzyl-qui ont CtC transformis en dCrivCs du 2-azido-2-dCsoxy-a-galactopyranoside de phCnyle avec de bons rendements, on a vCrifiC la compatibilitk de la deuxikme mCthode avec la prtsence d'un groupe hydroxyle libre et de divers groupes protecteurs. Dans la deuxikme Ctape, l'hydrolyse de ces sClCnoglycosides fournit divers ...

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Section: Resultssupporting

confidence: 89%

Preparation of diversely protected 2-azido-2-deoxyglycopyranoses from glycals

Czernecki¹,

Ayadi²

1995

Can. J. Chem.

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“…17,18 After protection of the primary hydroxyl group at C-6 of 4 as triphenylmethyl ether yielding 5 (Scheme 2), 19,20 the hydroxyl group at C-2 was methylated affording 6 . 21 All temporary protecting groups of 6 were then removed with aqueous acetic acid affording 7 and, after perbenzylation, 8 . Treatment of 8 with N -bromosuccinimide in aqueous acetone removed the anomeric thiotolyl group yielding 9 as an intermediate that was typically not isolated, but immediately subjected to Swern oxidation with acetic anhydride in DMSO affording galactonolactone ( 3b ).…”

Section: Resultsmentioning

confidence: 99%

“…21 Sodium hydride (0.14 g, 3.600 mmol, 2 eq) was added to a solution of 5 (1.00 g, 1.800 mmol) in 10 mL THF at 0 °C. After 5 min, methyl iodide (0.51 g, 3.600 mmol, 2.00 eq) was added to the suspension in the cold.…”

Section: Methodsmentioning

confidence: 99%

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Illuminating the binding interactions of galactonoamidines during the inhibition of β-galactosidase (E. coli)

Fan

Pickens

Striegler

et al. 2016

Bioorganic & Medicinal Chemistry

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Several galactonoamidines were previously identified as very potent competitive inhibitors that exhibit stabilizing hydrophobic interactions of the aglycon in the active site of β-galactosidase (A. oryzae). To elucidate the contributions of the glycon to the overall inhibition ability of the compounds, three glyconoamidine derivatives with alteration in the glycon at C-2 and C-4 were synthesized and evaluated herein. All amidines are competitive inhibitors of β-galactosidase (E. coli) and show significantly reduced inhibition ability when compared to the parent. The results highlight strong hydrogen-bonding interactions between the hydroxyl group at C-2 of the amidine glycon and the active site of the enzyme. Slightly weaker H-bonds are promoted through the hydroxyl group at C-4. The inhibition constants were determined to be picomolar for the parent galactonoamidine, and nanomolar for the designed derivatives rendering all glyconooamidines very potent inhibitors of glycosidases albeit the derivatized amidines show up to 700-fold lower inhibition activity than the parent.

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“…Phenyl 2,6-di-O-benzyol-3,4-O-isopropylidene-1-thio-b-D-galactopyranoside (700 mg, 1.34 mmol) [85] was dissolved in 90 % acetic acid (6 mL). The mixture was stirred at 90 8C for 3 h. The solvent was removed, and the residue was azeotroped with toluene.…”

Section: Discussionmentioning

confidence: 99%

Carbohydrate Array Analysis of Anti‐Tn Antibodies and Lectins Reveals Unexpected Specificities: Implications for Diagnostic and Vaccine Development

Manimala

Jain³

et al. 2005

ChemBioChem

103

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The Tn antigen is a carbohydrate antigen expressed in most carcinomas, during embryogenesis, on pathogenic parasites, and on HIV. It has been evaluated extensively as a potential diagnostic marker and several Tn-based vaccines are in clinical trials. Based on discrepancies in the literature regarding Tn expression, we began to question whether antibodies and lectins used routinely to detect the Tn antigen were providing accurate information. To investigate this possibility, a carbohydrate microarray and a highly sensitive assay were developed and three frequently used Tn receptors (HBTn1, Bric111, and VVL-B4) were evaluated. Carbohydrate-array analysis revealed unexpected cross-reactivity with other human carbohydrate epitopes. VVL-B4 bound the Tn antigen, GalNAcalpha1-6Gal, and GalNAcalpha1-3Gal. Bric111 bound the Tn antigen, blood group A, GalNAcalpha1-6Gal, and GalNAcalpha1-3Gal. HBTn1 showed the best selectivity, but still displayed moderate binding to blood group A. Implications for the development of Tn-based diagnostics and vaccines are discussed.

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Preparation of pyranoid glycal derivatives from phenyl thioglycosides and glycosyl phenyl sulphones

Cited by 83 publications

References 36 publications

Preparation of diversely protected 2-azido-2-deoxyglycopyranoses from glycals

Preparation of diversely protected 2-azido-2-deoxyglycopyranoses from glycals

Illuminating the binding interactions of galactonoamidines during the inhibition of β-galactosidase (E. coli)

Carbohydrate Array Analysis of Anti‐Tn Antibodies and Lectins Reveals Unexpected Specificities: Implications for Diagnostic and Vaccine Development

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