Synthetic UDP-Furanoses as Potent Inhibitors of Mycobacterial Galactan Biogenesis

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ISI Web of Knowledge Page 1 (Articles 1 -- 26) [1] Record 1 of 26 Author(s): Peltier, P (Peltier, Pauline); Belanova, M (Belanova, Martina); Dianiskova, P (Dianiskova, Petronela); Zhou, RK (Zhou, Ruokun); Zheng, RB (Zheng, Ruixiang Blake); Pearcey, JA (Pearcey, Jean A.); Joe, M (Joe, Maju); Brennan, PJ (Brennan, Patrick J.); Nugier-Chauvin, C (Nugier-Chauvin, Caroline); Ferrieres, V (Ferrieres, Vincent); Lowary, TL (Lowary, Todd L.); Daniellou, R (Daniellou, Richard); Mikusova, K (Mikusova, Katarina) Title: Synthetic UDP-Furanoses as Potent Inhibitors of Mycobacterial Galactan Biogenesis Source: CHEMISTRY & BIOLOGY, 17 (12): 1356-1366 DEC 22 2010 Abstract: UDP-galactofuranose (UDP-Galf) is a substrate for two types of enzymes, UDP-galactopyranose mutase and galactofuranosyltransferases, which are present in many pathogenic organisms but absent from mammals. In particular, these enzymes are involved in the biosynthesis of cell wall galactan, a polymer essential for the survival of the causative agent of tuberculosis, Mycobacterium tuberculosis. We describe here the synthesis of derivatives of UDP-Galf modified at C-5 and C-6 using a chemoenzymatic route. In cell-free assays, these compounds prevented the formation of mycobacterial galactan, via the production of short "dead-end" intermediates resulting from their incorporation into the growing oligosaccharide chain. Modified UDP-furanoses thus constitute novel probes for the study of the two classes of enzymes involved in mycobacterial galactan assembly, and studies with these compounds may ultimately facilitate the future development of new therapeutic agents against tuberculosis. ISSN: 1074-5521 DOI: 10.1016/j.chembiol.2010.10.014 Record 2 of 26 Author(s): Bellomo, A (Bellomo, Ana); Daniellou, R (Daniellou, Richard); Plusquellec, D (Plusquellec, Daniel) Title: Allylation of cyclohexanones in aqueous media and influence of facial amphiphilic fructopyranosides Source: TETRAHEDRON LETTERS, 51 (38): 4934-4936 SEP 22 2010 Abstract: The indium-catalyzed allylation reaction was performed in good yields and short reaction time with various cyclohexanones in water. Aqueous facial amphiphilic carbohydrates solutions were also screened for their potency to modify the stereochemical outcome of the reaction. (C) 2010 Elsevier Ltd. All rights reserved. ISSN: 0040-4039 DOI: 10.1016/j.tetlet.2010.07.028 Record 3 of 26 Author(s): Dureau, R (Dureau, Remy); Robert-Gangneux, F (Robert-Gangneux, Florence); Gangneux, JP (Gangneux, Jean-Pierre); Nugier-Chauvin, C (Nugier-Chauvin, Caroline); Legentil, L (Legentil, Laurent); Daniellou, R (Daniellou, Richard); Ferrieres, V (Ferrieres, Vincent) Title: Synthetic UDP-furanoses inhibit the growth of the parasite Leishmania Source: CARBOHYDRATE RESEARCH, 345 (10): 1299-1305 Sp. Iss. SI JUL 2 2010 Conference Title: 15th European Carbohydrate Symposium Conference Date: JUL 19-24, 2009 Conference Location: Vienna, AUSTRIA Abstract: The chemical synthesis of UDP-6-NHAc-6-deoxy-Galf was performed and it led to the isolation of both pure anomers. They were then evaluated together with the previously prepared UDP-furanoses for their anti-parasitic properties against Leishmania donovani promastigotes, one of the agents responsible for visceral leishmaniasis. Amongst them, the unnatural 1,2-trans UDP-6-NHAc-Galf demonstrated a high potency in inhibiting the growth of the parasite. (C) 2010 Elsevier Ltd. All rights reserved.

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ISSN: 0008-6215 DOI: 10.1016/j.carres.2010.02.020 Record 4 of 26 Author(s): Sylla, B (Sylla, Balla); Descroix, K (Descroix, Karine); Pain, C (Pain, Christophe); Gervaise, C (Gervaise, Cedric); Jamois, F (Jamois, Frank); Yvin, JC (Yvin, Jean-Claude); Legentil, L (Legentil, Laurent); NugierChauvin, C (Nugier-Chauvin, Caroline); Daniellou, R (Daniellou, Richard); Ferrieres, V (Ferrieres, Vincent) Title: Double diastereoselection explains limitations in synthesizing mannose-containing beta-(1,3)-glucans Source: CARBOHYDRATE RESEARCH, 345 (10): 1366-1370 Sp. Iss. SI JUL 2 2010 Conference Title: 15th European Carbohydrate Symposium Conference Date: JUL 19-24, 2009 Conference Location: Vienna, AUSTRIA Abstract: It is known that 3-O-glycosylation of glucosidic acceptors bearing acyl groups in the 4 and 6 positions instead of a 4,6-O-benzylidene ring mainly affords a-glycosides. Described here is an unexpected stereochemical outcome for elongation at glucose O-3 of a beta-D-Glcp-(1 -> 3)-alpha-D-Manp disaccharide using peracetylated ethyl thioglucoside as a donor. This unexpected reaction was correlated with match-mismatch effects, as shown by efficient coupling of the same acceptor by a donor of L-configuration. (C) 2010 Elsevier Ltd. All rights reserved. ISSN: 0008-6215 DOI: 10.1016/j.carres.2010.04.018 Record 5 of 26 Author(s): Chlubnova, I (Chlubnova, Ilona); Filipp, D (Filipp, Dominik); Spiwok, V (Spiwok, Vojtech); Dvorakova, H (Dvorakova, Hana); Daniellou, R (Daniellou, Richard); Nugier-Chauvin, C (Nugier-Chauvin, Caroline); Kralova, B (Kralova, Blanka); Ferrieres, V (Ferrieres, Vincent) Title: Enzymatic synthesis of oligo-D-galactofuranosides and L-arabinofuranosides: from molecular dynamics to immunological assays Source: ORGANIC & BIOMOLECULAR CHEMISTRY, 8 (9): 2092-2102 2010 Abstract: D-Galactofuranosyl-containing conjugates are ubiquitous in many pathogenic microorganisms, but completely absent from mammals. As they may constitute interesting pharmacophores, recent works have been dedicated to their preparation. Besides well-reported chemical procedures, enzymatic approaches are still limited, mainly due to the lack of the corresponding biocatalysts. Based on the similarity between chemical structures, the arabinofuranosyl hydrolase Araf51 from Clostridium thermocellum was expected to recognize both the L-Araf motif and its D-Galf analogue. Molecular dynamics and STD-NMR were firstly used to confirm this hypothesis and increase our knowledge of the active site. Interestingly, this arabinofuranosidase was not only able to hydrolyze galactosyl derivatives, but was also really efficient in catalyzing oligomerisations using p-nitrophenyl furanosides as donors. The structures of the products obtained were determined using mass spectrometry and NMR. Amongst them, all the possible regioisomers of di-arabino and -galactofuranosides were synthesized, and the ratio of each regioisomer was easily tuned with respect to the reaction time. Especially, the galactofuranobioside displaying the biologically relevant sequence beta-D-Galf-(1,6)-beta-D-Galf was enzymatically prepared for the first time. All fractions going from di- to penta-arabino-and galactofuranosides were tested for their ability in eliciting the production of TNF-alpha. Interesting immunological properties were observed with arabinofuranosides as short as three sugar residues. ISSN: 1477-0520 DOI: 10.1039/b926988f Record 6 of 26

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Author(s): Chlubnova, I (Chlubnova, I.); Chlubnova, I (Chlubnova, I.); Daniellou, R (Daniellou, R.); Spiwok, V (Spiwok, V.); Nugier-Chauvin, C (Nugier-Chauvin, C.); Dvorakova, H (Dvorakova, H.); Kralova, B (Kralova, B.); Ferrieres, V (Ferrieres, V.) Title: Neoglycoconjugates - Mimics of immunogenic pathogen structures Source: FEBS JOURNAL, 276: 178-178 Suppl. 1 JUL 2009 Conference Title: 34th Congress of the Federation-of-European-Biochemical-Societies Conference Date: JUL 04-09, 2009 Conference Location: Prague, CZECH REPUBLIC ISSN: 1742-464X Record 7 of 26 Author(s): Lunackova, T (Lunackova, T.); Kralova, B (Kralova, B.); Daniellou, R (Daniellou, R.); Ferrieres, V (Ferrieres, V.); Purkrtova, Z (Purkrtova, Z.) Title: Expression and purification of microbial galactofuranosyltransferases Source: FEBS JOURNAL, 276: 325-325 Suppl. 1 JUL 2009 Conference Title: 34th Congress of the Federation-of-European-Biochemical-Societies Conference Date: JUL 04-09, 2009 Conference Location: Prague, CZECH REPUBLIC ISSN: 1742-464X Record 8 of 26 Author(s): Collen, PN (Collen, Pi Nyvall); Lemoine, M (Lemoine, Maud); Daniellou, R (Daniellou, Richard); Guegan, JP (Guegan, Jean-Paul); Paoletti, S (Paoletti, Sergio); Helbert, W (Helbert, William) Title: Enzymatic Degradation of kappa-Carrageenan in Aqueous Solution Source: BIOMACROMOLECULES, 10 (7): 1757-1767 JUL 2009 Abstract: Enzymatic degradation of standard kappa-carrageenan and the low-gelling hybrid kappa-/mu-carrageenan were conducted using recombinant Pseudoalteromonas carrageenovora kappa-carrageenase. The initial velocity of the enzyme was determined as, a function of varying Tris or Nal concentrations and at constant 200 mM cosolutes concentration, adjusting Nal and Tris concentrations accordingly. In both cases, we observed strong inhibition of the enzyme with increasing amounts of iodide. The characterization of the kappa- and kappa-/mu-carrageenan ordering by optical rotation and the visualization of iodide binding on carrageenan by I-127 NMR revealed that inhibition was not caused by the disordered-ordered transition of carrageenan in Nal, but by iodide binding. These results were confirmed by analysis of the degradation products by gel permeation chromatography. Degradation of carrageenan in the disordered state led to a rapid decrease in molecular mass and the production of all possible neo-kappacarrabiose oligomers. In the ordered conformation, the degradation kinetics, the decrease of average molecular weight, and the chain population distribution of degradation products varied with iodide concentration. These observations were interpreted to be the result of increasing amounts of bound iodide on carrageenan helices that, in turn, impede enzyme catalysis. Based on these results, we propose a single-helix ordered conformation state for kappa-carrageenan and reject the previously advocated double-helix model. ISSN: 1525-7797 DOI: 10.1021/bm9001766 Record 9 of 26 Author(s): Gervaise, C (Gervaise, Cedric); Daniellou, R (Daniellou, Richard); Nugier-Chauvin, C (Nugier-Chauvin, Caroline); Ferrieres, V (Ferrieres, Vincent) Title: Influencing the regioselectivity of lipase-catalyzed hydrolysis with [bmim]PF6

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Source: TETRAHEDRON LETTERS, 50 (18): 2083-2085 MAY 6 2009 Abstract: An easy preparation of mono-deprotected thioglucopyramosides via a selective Candica cylindracea lipase-catalyzed hydrolysis of a commercially available peracetylated precursor is described. Especially, ethyl 2,3,4tri-O-acetyl-1-thio-beta-D-glucopyranoside and ethyl 2,3,6-tri-O-acetyl-1-thio-beta-D-glucopyranoside were obtained in 100% and 54% isolated yields, respectively. The influence of the ratio of [bmim]PF6/buffer towards the regioselectivity of the deacetylation step and the acyl migration is discussed. (c) 2009 Elsevier Ltd. All rights reserved. ISSN: 0040-4039 DOI: 10.1016/j.tetlet.2009.02.119 Record 10 of 26 Author(s): Eppe, G (Eppe, Guillaume); Peltier, P (Peltier, Pauline); Daniellou, R (Daniellou, Richard); NugierChauvin, C (Nugier-Chauvin, Caroline); Ferrieres, V (Ferrieres, Vincent); Vincent, SP (Vincent, Stephane P.) Title: Probing UDP-galactopyranose mutase binding pocket: A dramatic effect on substitution of the 6-position of UDP-galactofuranose Source: BIOORGANIC & MEDICINAL CHEMISTRY LETTERS, 19 (3): 814-816 FEB 1 2009 Abstract: UDP-galactopyranose mutase (UGM) catalyzes the isomerization of UDP-galactopyranose (UDP-Galp) into UDP-galactofuranose (UDP-Galf), an essential step of the mycobacterial cell wall biosynthesis. UDP-(6-deoxy6-fluoro)-D-galactofuranose 1 was tested as substrate of UGM. Turnover could be observed by HPLC. The k(cat) (7.4 s (1)) and the K-m (24 mM) of 1 were thus measured and compared with those of UDP- Galf and other fluorinated analogs. The presence of the fluorine atom at the 6-position had a moderate effect on the rate of the reaction but a huge one on the interactions between the enzyme and its substrate. This result demonstrated that key interactions occur at the vicinity of the 6-position of UDPgalactose in the Michaelis complex. (C) 2009 Elsevier Ltd. All rights reserved. ISSN: 0960-894X DOI: 10.1016/j.bmcl.2008.12.014 Record 11 of 26 Author(s): Peltier, P (Peltier, Pauline); Guegan, JP (Guegan, Jean-Paul); Daniellou, R (Daniellou, Richard); NugierChauvin, C (Nugier-Chauvin, Caroline); Ferrieres, V (Ferrieres, Vincent) Title: Stereoselective Chemoenzymatic Synthesis of UDP-1,2-cis-furanoses from alpha,beta-Furanosyl 1-Phosphates Source: EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, (35): 5988-5994 DEC 2008 Abstract: The biosynthesis of furanosyl-containing glycoconjugates is poorly described, mainly due to the lack of UDP-furanoses. Here we present our effort to synthesize rare nucleoticle-sugars with the aid of a multiple-enzyme system, notably including galactose-1-phosphate uridylyltransferase. Firstly, STD-NMR techniques were used to probe the broad substrate specificity of this particular enzyme. The chemical synthesis of the needed furanosyl 1-phosphate starting materials was then performed with unprotected thioimidoyl donors. This led to the first stereoselective chemoenzymatic syntheses of UDP-beta-L-arabinofuranose, UDP-alpha-D-fucofuranose and UDP-alpha-D-6F-galactofuranose from starting mixtures of sugar-phosphates. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) ISSN: 1434-193X DOI: 10.1002/ejoc.200800742 Record 12 of 26 Author(s): Timmons, SC (Timmons, Shannon C.); Hui, JPM (Hui, Joseph P. M.); Pearson, JL (Pearson, Jessica L.); Peltier, P (Peltier, Pauline); Daniellou, R (Daniellou, Richard); Nugier-Chauvin, C (Nugier-Chauvin, Caroline); Soo, EC (Soo, Evelyn C.); Syvitski, RT (Syvitski, Ray T.); Ferrieres, V (Ferrieres, Vincent); Jakeman, DL (Jakeman,

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David L.) Title: Enzyme-catalyzed synthesis of furanosyl nucleotides (vol 10, pg 161, 2008) Source: ORGANIC LETTERS, 10 (17): 3931-3931 SEP 4 2008 ISSN: 1523-7060 DOI: 10.1021/ol801686c Record 13 of 26 Author(s): Jakeman, DL (Jakeman, David L.); Young, JL (Young, Jessica L.); Huestis, MP (Huestis, Malcolm P.); Peltier, P (Peltier, Pauline); Daniellou, R (Daniellou, Richard); Nugier-Chauvin, C (Nugier-Chauvin, Caroline); Ferrieres, V (Ferrieres, Vincent) Title: Engineering ribonucleoside triphosphate specificity in a thymidylyltransferase Source: BIOCHEMISTRY, 47 (33): 8719-8725 AUG 19 2008 Abstract: Nature's glycosylation catalysts, glycosyltransferases, indirectly manipulate and control many important biological processes by transferring sugar nucleotide donors onto acceptors. Challenging chemical synthesis impedes synthetic access to sugar nucleotides and limits the study of many glycosyltransferases. Enzymatic access to sugar nucleotides is a rapidly expanding avenue of research, limited only by the substrate specificity of the enzyme. We have explored the promiscuous thymidylyltransferase from Streptococcus pneumoniae, Cps2L, and enhanced its uridylyltransferase and guanidyltransferase activities by active site engineering. Mutagenesis at position Q24 resulted in a variant with 10-, 3-, and 2-fold enhancement of UDP-glucosamine, UDP-mannose, and UDP-Nacetylglucosamine production, respectively. New catalytic activities were observed for the Cps2L variant over the wild-type enzyme, including the formation of GDP-mannose. The variant was evaluated as a catalyst for the formation of a series of dTDP- and UDP-furanoses and notably produced dTDP-Galf in 90% yield and UDP-Araf in 30% yield after 12 h. A series of 3-O-alkylglucose I-phosphates were also evaluated as substrates, and notable conversions to UDP-3-O-methylglucose and UDP-3-O-dodecylglucose were achieved with the variant but not the wild-type enzyme. The Q24S variant also enhanced essentially all thymidylyltransferase activities relative to the wild-type enzyme. Comparison of active sites of uridylyltransferases and thymidylyltransferases with products bound indicate the Q24S variant to be a new approach in broadening nucleotidylyltransferase activity. ISSN: 0006-2960 DOI: 10.1021/bi800978u Record 14 of 26 Author(s): Peltier, P (Peltier, Pauline); Euzen, R (Euzen, Ronan); Daniellou, R (Daniellou, Richard); NugierChauvin, C (Nugier-Chauvin, Caroline); Ferrieres, V (Ferrieres, Vincent) Title: Recent knowledge and innovations related to hexofuranosides: structure, synthesis and applications Source: CARBOHYDRATE RESEARCH, 343 (12): 1897-1923 AUG 11 2008 Conference Title: 14th European Carbohydrate Symposium (EUROCARB 14) Conference Date: SEP 02-07, 2007 Conference Location: Lubeck, GERMANY Abstract: Hexofuranosides are widely spread in nature, and notably in numerous pathogenic microorganisms. This particular five-membered ring for hexosides leads to novel biological properties and, as usual in glycochemistry, to completely different reactivity and selectivity. Far from being exhaustive, this review will first focus on the structure of the oligosaccharidic part of hexofuranosyl conjugates found in natural sources. Original syntheses will then be presented, stressing more particularly on the development of chemical and chemo-enzymatic tools for the access to 1,2-trans or 1,2-cis linkages. Finally, innovative applications related to biological, chemical and physicochemical fields for both natural and synthetic hexofuranosyl compounds will be described. (C) 2008 Elsevier Ltd. All rights reserved. ISSN: 0008-6215

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DOI: 10.1016/j.carres.2008.02.010 Record 15 of 26 Author(s): Peltier, P (Peltier, Pauline); Daniellou, R (Daniellou, Richard); Roisnel, T (Roisnel, Thierry); NugierChauvin, C (Nugier-Chauvin, Caroline); Ferrieres, V (Ferrieres, Vincent) Title: 4-Nitrophenyl alpha-L-rhamnopyranoside hemihydrate Source: ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE, 64: O379-U1778 Part 2 FEB 2008 Abstract: In the title compound, C12H15NO7 center dot 0.5H(2)O, there are two independent molecules in the asymmetric unit, together with one water molecule. The pyranoside rings each have close to a C-1(4) chair conformation and the nitro groups are almost coplanar with the benzene rings. The water molecule links the two independent molecules through O-H center dot center dot center dot O hydrogen bonds. All the hydroxyl groups are involved in hydrogen-bond interactions, giving rise to a three-dimensional network. ISSN: 1600-5368 DOI: 10.1107/S1600536807068195 Record 16 of 26 Author(s): Timmons, SC (Timmons, Shannon C.); Hui, JPM (Hui, Joseph P. M.); Pearson, JL (Pearson, Jessica L.); Peltier, P (Peltier, Pauline); Daniellou, R (Daniellou, Richard); Nugier-Chauvin, C (Nugier-Chauvin, Caroline); Soo, EC (Soo, Evelyn C.); Syvitski, RT (Syvitski, Ray T.); Ferrieres, V (Ferrieres, Vincent); Jakeman, DL (Jakeman, David L.) Title: Enzyme-catalyzed synthesis of furanosyl nucleotides Source: ORGANIC LETTERS, 10 (2): 161-163 JAN 17 2008 Abstract: A bacterial alpha-D-glucopyranosyl-1-phosphate thymidylyltransferase was found to couple four hexofuranosyl-1-phosphates, as well as a pentofuranosyl-1-phosphate, with deoxythymidine 5'-triphosphate, providing access to furanosyl nucleotides. The enzymatic reaction mixtures were analyzed by electrospray ionization mass spectrometry and NMR spectroscopy to determine the anomeric stereochemistry of furanosyl nucleotide products. This is the first demonstration of a nucleotidylyltransferase discriminating between diastereomeric mixtures of sugar-1-phosphates to produce stereopure, biologically relevant furanosyl nucleotides. ISSN: 1523-7060 DOI: 10.1021/ol7023949 Record 17 of 26 Author(s): Peltier, P (Peltier, Pauline); Daniellou, R (Daniellou, Richard); Nugier-Chauvin, C (Nugier-Chauvin, Caroline); Ferrieres, V (Ferrieres, Vincent) Title: Versatile synthesis of rare nucleotide furanoses Source: ORGANIC LETTERS, 9 (25): 5227-5230 DEC 6 2007 Abstract: Direct activation of unprotected thioimidoyl furanosides yielded in only one step and few minutes a panel of rare uridine 5'-diphosphofuranoses. Diastereoselectivity of the reaction was tightly connected with reaction time, temperature, and nature of the furanosyl donor. This approach was totally selective since no ring expansion from the initial five-membered ring to the more stable pyranose form was observed. ISSN: 1523-7060 DOI: 10.1021/ol702392x Record 18 of 26

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Author(s): Gervaise, C (Gervaise, Cedric); Daniellou, R (Daniellou, Richard); Roisnel, T (Roisnel, Thierry); Nugier-Chauvin, C (Nugier-Chauvin, Caroline); Ferrieres, V (Ferrieres, Vincent) Title: Benzyl 4,6-di-O-acetyl-2-O-benzoyl-beta-d-glucopyranoside Source: ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE, 63: O2286-O2288 Part 5 MAY 2007 Abstract: In the crystal structure of the title compound, C24H26O9, molecules are linked by O-H center dot center dot center dot O hydrogen bonds, creating a chain of hydrogen-bonded molecules in the c-axis direction. ISSN: 1600-5368 DOI: 10.1107/S1600536807015255 Record 19 of 26 Author(s): Daniellou, R (Daniellou, Richard); Zheng, HY (Zheng, Hongyan); Langill, DM (Langill, David M.); Sanders, DAR (Sanders, David A. R.); Palmer, DRJ (Palmer, David R. J.) Title: Probing the promiscuous active site of myo-inositol dehydrogenase using synthetic substrates, homology modeling, and active site modification Source: BIOCHEMISTRY, 46 (25): 7469-7477 JUN 26 2007 Abstract: The active site of myo-inositol dehydrogenase (IDH, EC 1.1.1.18) from Bacillus subtilis recognizes a variety of mono- and disaccharides, as well as 1L-4-O-substituted inositol derivatives. It catalyzes the NAD(+)-dependent oxidation of the axial alcohol of these substrates with comparable kinetic constants. We have found that 4-O-p-toluenesulfonyl-myo-inositol does not act as a substrate for IDH, in contrast to structurally similar compounds such as those bearing substituted benzyl substituents in the same position. X-ray crystallographic analysis of 4-O-p-toluenesulfonyl-myo-inositol and 4-O-(2-naphthyl)methyl-myo-inositol, which is a substrate for IDH, shows a distinct difference in the preferred conformation of the aryl substituent. Conformational analysis of known substrates of IDH suggests that this conformational difference may account for the difference in reactivity of 4-O-p-toluenesulfonyl-myo-inositol in the presence of IDH. A sequence alignment of IDH with the homologous glucose-fructose oxidoreductase allowed the construction of an homology model of inositol dehydrogenase, to which NADH and 4-O-benzyl-scyllo-inosose were docked and the active site energy minimized. The active site model is consistent with all experimental results and suggests that a conserved tyrosine-glycine-tyrosine motif forms the hydrophobic pocket adjoining the site of inositol recognition. Y233F and Y235F retain activity, while Y233R and Y235R do not. A histidine-aspartate pair, H176 and D172, are proposed to act as a dyad in which H176 is the active site acid/base. The enzyme is inactivated by diethyl pyrocarbonate, and the mutants H176A and D172N show a marked loss of activity. Kinetic isotope effect experiments with D172N indicate that chemistry is rate-determining for this mutant. ISSN: 0006-2960 DOI: 10.1021/bi700281x Record 20 of 26 Author(s): Lopez, G (Lopez, Gerald); Daniellou, R (Daniellou, Richard); O'Donohue, M (O'Donohue, Michael); Ferrieres, V (Ferrieres, Vincent); Nugier-Chauvin, C (Nugier-Chauvin, Caroline) Title: Thioimidoyl furanosides as first inhibitors of the alpha-L-arabinofuranosidase AbfD3 Source: BIOORGANIC & MEDICINAL CHEMISTRY LETTERS, 17 (2): 434-438 JAN 15 2007 Abstract: Two sets of five thioimidoyl alpha-L-arabino- and beta-D-galactofuranosides were designed, synthesized and subjected to docking studies to evaluate their ability to be recognized by the active site of the alphaL-arabinofuranosidase AbfD3. Further in vitro assays showed that the targeted furanosides are the first potent inhibitors of this furanosyl hydrolase and that the most efficient one, the thiazolyl alpha-L-arabinofuranoside 1, is a competitive inhibitor having a K-I of 1.4 mu M. (c) 2006 Elsevier Ltd. All rights reserved. ISSN: 0960-894X DOI: 10.1016/j.bmcl.2006.10.032

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Record 21 of 26 Author(s): Daniellou, R (Daniellou, Richard); Quail, JW (Quail, J. Wilson); Palmer, DRJ (Palmer, David R. J.) Title: 4/6-O-(p-Tolylsulfonyl)-myo-inositol Source: ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE, 62: O4880-O4881 Part 11 NOV 2006 Abstract: The title compound, C13H18O8S, packs in hydrogen-bonded layers in the crystal structure; the aromatic ring subtends an angle of 80.09 (14)degrees to the plane describing the inositol chair. ISSN: 1600-5368 DOI: 10.1107/S160053680604044X Record 22 of 26 Author(s): Daniellou, R (Daniellou, Richard); Palmer, DRJ (Palmer, David R. J.) Title: Appel-Lee synthesis of glycosyl inositols, substrates for inositol dehydrogenase from Bacillus subtilis Source: CARBOHYDRATE RESEARCH, 341 (12): 2145-2150 SEP 4 2006 Abstract: We recently reported that inositol dehydrogenase (EC 1.1.1.18) from Bacillus subtilis can catalyze the highly stereoselective oxidation Of IL-4-O-substituted myo-inositol derivatives, as well as disaccharides melibiose and isomaltose, but not gentiobiose or maltose, consistent with the requirement of an alpha-(1 -> 6) linkage. We believed that the enzyme might therefore catalyze efficient stereoselective oxidation of the appropriate alpha-linked glycosyl inositols. We have synthesized alpha-D-glucopyranosyl-(1 -> 4)-(DL)-MYO-inositol and alphaD-galactopyranosyl-(1 -> 4)-(DL)-myo-inositol using the Appel-Lee protocol to couple benzyl-protected glycosyl donors to protected inositols. This method failed in our hands using glycosyl donors derived from D-mannose and 2-azido-2-deOXY-D-glucose. When myo-inositol 1, 3,5-monoorthoformate is used as the acceptor, the reaction is regiospecific for the 4/6-position. We report here the mildest conditions known for the removal of the orthoformate group. 2-Azido-2-deoxy-alpha-D-glucopyranosyl-(1-4)-(DL)-myo-inositol was synthesized using the trichloroacetimidate derivative as the donor, and all three pseudodisaccharides were substrates for inositol dehydrogenase. The glucopyranosyl and galactopyranosyl derivatives displayed apparent second-order rate constants comparable to that of myo-inositol. (c) 2006 Elsevier Ltd. All rights reserved. ISSN: 0008-6215 DOI: 10.1016/j.carres.2006.05.001 Record 23 of 26 Author(s): Daniellou, R; Zheng, HY; Palmer, DRJ Title: Kinetics of the reaction catalyzed by inositol dehydrogenase from Bacillus subtilis and inhibition by fluorinated substrate analogs Source: CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 84 (4): 522-527 APR 2006 Abstract: Inositol dehydrogenase (EC 1.1.1.18) from Bacillus subtilis catalyzes the oxidation of myo-inositol to scyllo-inosose by transfer of the equatorial hydride of the substrate to NAD(+). This is a key enzyme in the metabolism of myo-inositol, a primary carbon source for soil bacteria. In light of our recent discovery that the enzyme has a broad substrate spectrum while maintaining high stereoselectivity, we seek a more thorough understanding of the enzyme and its active site. We have examined the kinetics of the recombinant enzyme, and synthesized fluorinated substrate analogues as competitive inhibitors. We have evaluated all rate constants in the ordered, sequential Bi Bi mechanism. No steady-state kinetic isotope effect is observed using myo-[2-H-2]-inositol, indicating that the chemical step of the reaction is not rate-limiting. We have synthesized the substrate analogs 2-deoxy-2-fluoro-myo-inositol, its equatorial analog 1-deoxy-1-fluoro-scyllo-inositol, the gem-difluorinated analog 1-deoxy-1,1-difluoro-scyllo-inositol, and the sugar analog alpha-D-glucosyl fluoride. Of these, 1-deoxy-1-fluoroscyllo-inositol showed no inhibition, while all others tested had K-i values comparable to the K-m values of the

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analogous substrates myo-inositol and alpha-D-glucose. ISSN: 0008-4042 DOI: 10.1139/V06-033 Record 24 of 26 Author(s): Daniellou, R; Le Narvor, C Title: Synthesis of GDP-fucose on a soluble support: A donor substrate for the fucosyltransferases Source: ADVANCED SYNTHESIS & CATALYSIS, 347 (14): 1863-1868 NOV 2005 Abstract: The synthesis of GDP-fucose on a poly(ethylene glycol)-based soluble support is described. Our strategy relies on the attachment of the 6-deoxy-6-thio-L-galactose onto the polymer via a thioether linkage, and its conversion to GDP-fucose using established methods. We thus obtained GDP-fucose bound to the polymer that was tested as an acceptor for the recombinant fucosyltranferase FucT-III. ISSN: 1615-4150 DOI: 10.1002/adsc.200505170 Record 25 of 26 Author(s): Daniellou, R; Phenix, CP; Tam, PH; Laliberte, MC; Palmer, DRJ Title: Stereoselective oxidation of protected inositol derivatives catalyzed by inositol dehydrogenase from Bacillus subtilis Source: ORGANIC & BIOMOLECULAR CHEMISTRY, 3 (3): 401-403 2005 Abstract: Inositol dehydrogenase (EC 1.1.1.18) from Bacillus subtilis is shown to have a nonpolar cavity adjacent to the active site, allowing racemic protected inositol derivatives such as 4-O-benzyl-myo-inositol to be recognized with very high apparent stereoselectivity. ISSN: 1477-0520 DOI: 10.1039/b417757f Record 26 of 26 Author(s): Renaudie, L; Daniellou, R; Auge, C; Le Narvor, C Title: Enzymatic supported synthesis of lacto-N-neotetraose using dendrimeric polyethylene glycol Source: CARBOHYDRATE RESEARCH, 339 (3): 693-698 FEB 25 2004 Abstract: The lacto-N-neotetraose tetrasaccharide was synthesized on a new dendrimeric support, based on polyethylene glycol. Starting from 1-thio-beta-D-lactose, the trisaccharide (2-acetamido-2-deoxy-beta-Dglucopyranosyl)-(1 --> 3)-O-beta-D-galactopyranosyl-(1 --> 4)-1-thio-beta-D-glucopyranose was obtained using Neisseria meningitidis beta-(1--> 3)-N-acetylglucosaminyltransferase according to a soluble synthesis approach, bound on the support and galactosylated using the milk beta-(1 --> 4)-galactosyl transferase to give after cleavage the tetrasaccharide lacto-N-neotetraose. (C) 2003 Elsevier Ltd. All rights reserved. ISSN: 0008-6215 DOI: 10.1016/j.carres.2003.11.017 ISI Web of Knowledge Page 1 (Articles 1 -- 26) [1] Acceptable Use Policy Copyright © 2008 Thomson Reuters

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