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The Relevance of Carbohydrate Hydrogen-Bonding Cooperativity Effects: A Cooperative 1,2-trans-Diaxial Diol and Amido Alcohol Hydrogen-Bonding Array as an Efficient Carbohydrate–Phosphate Binding Motif in Nonpolar Media

2002; Wiley; Volume: 8; Issue: 8 Linguagem: Inglês

10.1002/1521-3765(20020415)8

1521-3765

Eva Muñoz, Manuela López de la Paz, Jesús Jiménez‐Barbero, Gary Ellis, Marta Pérez‐Torralba, Cristina Vicent,

Enzyme Structure and Function

Chemistry – A European JournalVolume 8, Issue 8 p. 1908-1914 Full Paper The Relevance of Carbohydrate Hydrogen-Bonding Cooperativity Effects: A Cooperative 1,2-trans-Diaxial Diol and Amido Alcohol Hydrogen-Bonding Array as an Efficient Carbohydrate–Phosphate Binding Motif in Nonpolar Media Eva Maria Muñoz, Eva Maria Muñoz Instituto de Química Orgánica General CSIC, Juan de la Cierva 3, 28006 Madrid (Spain)Search for more papers by this authorManuela López de la Paz Dr., Manuela López de la Paz Dr. Instituto de Química Orgánica General CSIC, Juan de la Cierva 3, 28006 Madrid (Spain)Search for more papers by this authorJesús Jiménez-Barbero Dr., Jesús Jiménez-Barbero Dr. Instituto de Química Orgánica General CSIC, Juan de la Cierva 3, 28006 Madrid (Spain)Search for more papers by this authorGary Ellis Dr., Gary Ellis Dr. Instituto de Ciencia y Tecnología de Polímeros CSIC, Juan de la Cierva 3, 28006 Madrid (Spain)Search for more papers by this authorMarta Pérez, Marta Pérez Instituto de Química Orgánica General CSIC, Juan de la Cierva 3, 28006 Madrid (Spain)Search for more papers by this authorCristina Vicent Dr., Cristina Vicent Dr. [email protected] Instituto de Química Orgánica General CSIC, Juan de la Cierva 3, 28006 Madrid (Spain)Search for more papers by this author Eva Maria Muñoz, Eva Maria Muñoz Instituto de Química Orgánica General CSIC, Juan de la Cierva 3, 28006 Madrid (Spain)Search for more papers by this authorManuela López de la Paz Dr., Manuela López de la Paz Dr. Instituto de Química Orgánica General CSIC, Juan de la Cierva 3, 28006 Madrid (Spain)Search for more papers by this authorJesús Jiménez-Barbero Dr., Jesús Jiménez-Barbero Dr. Instituto de Química Orgánica General CSIC, Juan de la Cierva 3, 28006 Madrid (Spain)Search for more papers by this authorGary Ellis Dr., Gary Ellis Dr. Instituto de Ciencia y Tecnología de Polímeros CSIC, Juan de la Cierva 3, 28006 Madrid (Spain)Search for more papers by this authorMarta Pérez, Marta Pérez Instituto de Química Orgánica General CSIC, Juan de la Cierva 3, 28006 Madrid (Spain)Search for more papers by this authorCristina Vicent Dr., Cristina Vicent Dr. [email protected] Instituto de Química Orgánica General CSIC, Juan de la Cierva 3, 28006 Madrid (Spain)Search for more papers by this author First published: 16 April 2002 https://doi.org/10.1002/1521-3765(20020415)8:8 3.0.CO;2-JCitations: 19Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Graphical Abstract The use of cooperativity to achieve efficient binding of the hydrogen-bonding centres of sugar derivatives to the phosphate H-bonding motif has been studied (see figure). The energetic contribution to binding in nonpolar solvents has been evaluated. Abstract Carbohydrates with suitably positioned intramolecularly hydrogen-bonded hydroxyl and amide groups have the potential to act as efficient bidentate phosphate binders by taking advantage of σ- and/or σ,π-H-bonding cooperativity in nonpolar solvents. Donor–donor 1,2-trans-diaxial amido alcohol (1) and diol (3), in which one of the donor centres is cooperative, are very efficient carbohydrate–phosphate binding motifs. We have proven and quantified the key role of hydrogen-bonding centres indirectly involved in complexation, which serve to generate an intramolecular H-bond (six-membered cis H-bond) in 1 and 3. This motif enhances the donor nature of the H-bonding centres that are directly involved in complexation. A comparison of the thermodynamic parameters of the complexes formed between phosphate and a cooperative (1-Phos) or anti-cooperative (2-Phos) bidentate H-bonded motif of a carbohydrate has allowed us to quantify the energetic advantage of H-bonding cooperativity in CDCl3 and CDCl3/CCl4 (1:1.3) (ΔΔG °=−2.2 and −2.0 kcal mol−1, respectively). The solvent dependences of the entropy and enthalpy contributions to binding provide a valuable example of the delicate balance between entropy and enthalpy that can arise for a single process, providing effective cooperative binding in terms of ΔG °. Supporting Information Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2111/2002/f3615_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article. References 1 E. J. Rohr, Bioorganic Chemistry: Models and Applications, Vol. 184, Springer, Berlin, 1997. 2 2a S. Walker, J. Murnick, D. Kahne, J. Am. Chem. Soc. 1993, 115, 7954–7961; 2b G. Bifulco, A. Galeone, L. Gomez-Paloma, K. C. Nicolaou, W. J. Chazin, J. Am. Chem. Soc. 1996, 118, 8817–8824. 3 3a H. Pelmore, G. Eaton, M. C. R. Symons, J. Chem. Soc. Perkin Trans. 2 1992, 149–150; 3b A. G. Krishna, D. Balasubramanian, K. N. Ganesh, Biochem. Biophys. Res. Commun. 1994, 202, 204–210; 3c H. A. Tajmir-Riahi, M. Naoui, S. Diamantoglou, J. Biomol. Struct. Dynamics 1994, 12, 217–231. 4 For hydroxyl–phosphate binding, see: 4a S. Anderson, U. Neidlein, V. Gramlich, F. Diederich, Angew. Chem. 1995, 107, 1722–1715; Angew. Chem. Int. Ed. Engl. 1995, 34, 1596–1600; 4b M. Coterón, F. Hacket, H.-J. Schneider, J. Org. Chem. 1996, 61, 1429–1435; 4c M. Hendrix, P. B. Alper, E. S. Priestley, C.-H. Wong, Angew. Chem. 1997, 109, 119–122; Angew. Chem. Int. Ed. Engl. 1997, 36, 95–98; 4d G. Das, A. D. Hamilton, Tetrahedron Lett. 1997, 38, 3675–3678. 5 5a K. M. Depew, S. M. Zeman, S. H. Boyer, D. J. Denhart, N. Ikemoto, S. J. Danishefsty, D. M. Crothers, Angew. Chem. 1996, 108, 2972–2975; Angew. Chem. Int. Ed. Engl. 1996, 35, 2797–2801; 5b K. Toshima, R. Takano, Y. Maeda, M. Suzuki, A. Asai, S. Matsumura, Angew. Chem. 1999, 111, 3953–3955; Angew. Chem. Int. Ed. Engl. 1999, 38, 3733–3735; 5c H. Xuereb, M. Maletic, J. Gildersleeve, I. Pelczer, D. Kahne, J. Am. Chem. Soc. 2000, 122, 1883–1890. 6 M. López de la Paz, C. González, C. Vicent, Chem. Commun. 2000, 411–412. 7 7a M. López de la Paz, J. Jiménez-Barbero, C. Vicent, Chem. Commun. 1998, 465–466; 7b F. J. Luque, J. M. López, M. López de la Paz, C. Vicent, M. Orozco, J. Phys. Chem. 1998, 102, 6690–6696. 8 M. López de la Paz, G. Ellis, M. Pérez, J. Perkins, J. Jiménez-Barbero, C. Vicent, Eur. J. Org. Chem. 2002, 840–855. 9 Molecular mechanics calculations were carried out using Amber* within MACROMODEL 5.5, employing the GB/SA solvent model for CHCl3. We have modelled both possible bidentate phosphate complexes involving OH-2 and OH-4, and that involving OH-4 and NH-3 of sugar 1. According to the steric energy values, the second one is more stable. 10 Neither the sugar nor the phosphate dimerises in chloroform solution under the conditions used for the titration. 11 Downfield shifts of the OH and NH resonances, accompanied by upfield shifts of the CH resonances, allowed us to measure the Ka values. All stability constants were measured in triplicate and the ΔG ° values were found to be reproducible to within ±0.1 kcal mol−1. We thank Prof. C. Hunter (University of Sheffield) for kindly providing the fitting program. 12 Compound 6 is an exception. It forms a 1:2 complex (6-Phos). 13 The Ka value that we obtained for monoalcohol 8-Phos complex, 1.9 M−1, is of the same order as those measured by Schneider for aliphatic monohydroxyl compounds.[4b] 14 14a E. S. Stevens, N. Sugawara, G. M. Bonora, C. Toniolo, J. Am. Chem. Soc. 1980, 102, 7048–7050; 14b C. Huang, L. A. Cabell, V. Lynch, E. V. Anslyn, J. Am. Chem. Soc. 1992, 114, 1900–1901. 15 Mixing time for 1 (600 ms, 299 K), and 1-Phos (600 ms, 299 K). NOEs between the aromatic resonances (H2 and H5) of the phosphate and the alkyl methyl and methylene resonances of the ammonium salt confirmed the presence of the ionic pair. 16 IR spectra were recorded from dilute solutions in a fixed pathlength (0.1 mm) liquid cell with KBr windows. The spectra of Phos, the sugars, and the sugar–Phos complexes were ratioed to the background spectrum recorded with dry CH2Cl2 in the IR cell. 17 For sugar 2, the intermolecular association bands in the range 3400–3100 cm−1 are observed only very weakly as compared with those of the complex 1-Phos, which is to be expected considering the low saturation obtained for 2-Phos under these experimental conditions. For this reason, the observations in the region of the amide modes in 2 are inconclusive. However, by normalizing the spectra with respect to the intensity of the band due to the ester carbonyl group of the OBz moiety, a very slight reduction in the relative intensity of the amide II mode, characteristic of the NH bond, can be observed on going from 2 to 2-Phos. 18 18a G. A. Jeffrey, W. Saenger, Hydrogen Bonding in Biological Structures, Springer, Berlin, 1991; 18b H. Kleeberg, D. Klein, W. A. P. Luck, J. Phys. Chem. 1987, 91, 3200–3203; 18c G. Maes, J. Smets, J. Phys. Chem. 1993, 97, 1818–1825. 19 B. N. Craig, M. U. Janssen, B. M. Wichersham, D. M. Rabb, P. S. Chang, D. J. O'Leary, J. Org. Chem. 1996, 61, 9610–9613. 20 3J analysis of the 1H NMR spectra showed that all the compounds other than 4 exhibit 3J values consistent with the adoption of a chair conformation in CDCl3 and CDCl3/CCl4 solution: A. Rivera-Sagredo, J. Jiménez-Barbero, Carbohydr. Res. 1991, 215, 239–250. 21 NMR (CIS and temperature coefficients) and IR structural data (see above) confirmed the non-involvement of the amide in complexation. 22 The C2−NHCO bond rotation is more restricted than that about C2−OH. We cannot rule out the presence of a percentage of the H-bonded isomer in solution (O-H4→O-H2), which will be shifted upon binding to the favored H-bonding isomer (O-H2→O-H4). 23 Based on the study of Williams,[24] we have plotted the calculated limiting chemical shifts of the NH resonance at saturation for 1-Phos and 2-Phos in both solvent systems. The larger binding shift of the NH in 1 as compared to that in 2 is taken to imply stronger interaction with Phos. It emerged that the intermolecular NH–Phos H-bond in 1-Phos is cooperatively enhanced by the presence of a neighbouring interaction (the intramolecular H-bond) as compared to the same H-bonding motif in 2-Phos (Figure 2). The same holds true for the OH-4 resonance of 1-Phos compared to that of 2-Phos in the two media. 24 M. S. Searle, M. S. Westwell, D. H. Williams, J. Chem. Soc. Perkin Trans. 2 1995, 141–151. 25 H. Adams, F. J. Carver, C. A. Hunter, J. C. Morales, E. M. Seward, Angew. Chem. 1996, 108, 1628–1631; Angew. Chem. Int. Ed. Engl. 1996, 35, 1542. 26 W. C. Still, A. Tempczyk, R. C. Hawley, T. Hendrickson, J. Am. Chem. Soc. 1990, 112, 6127–6129. 27 The acid was prepared from the corresponding methyl ester.[28] 28 A. C. Hengge, W. W. Cleland, J. Am. Chem. Soc. 1991, 113, 5835–5841. Citing Literature Volume8, Issue8April 15, 2002Pages 1908-1914 ReferencesRelatedInformation