3 Approaches to Chemical Synthesis of Pectic Oligosaccharides
Sergey A. Nepogodiev
John Innes Centre, Department of Biological Chemistry, Norwich Research Park, Colney Lane, Norwich, NR4 7UH UK
Search for more papers by this authorRobert A. Field
John Innes Centre, Department of Biological Chemistry, Norwich Research Park, Colney Lane, Norwich, NR4 7UH UK
Search for more papers by this authorIben Damager
University of Copenhagen, Faculty of Life Sciences, Department of Plant Biology and Biotechnology, Frederiksberg, Denmark
Search for more papers by this authorSergey A. Nepogodiev
John Innes Centre, Department of Biological Chemistry, Norwich Research Park, Colney Lane, Norwich, NR4 7UH UK
Search for more papers by this authorRobert A. Field
John Innes Centre, Department of Biological Chemistry, Norwich Research Park, Colney Lane, Norwich, NR4 7UH UK
Search for more papers by this authorIben Damager
University of Copenhagen, Faculty of Life Sciences, Department of Plant Biology and Biotechnology, Frederiksberg, Denmark
Search for more papers by this authorAbstract
Many aspects of pectin biosynthesis and the physical properties of pectic polysaccharides can be better understood with the aid of small, well-defined oligosaccharide fragments of these macromolecules. Synthetic chemists have contributed to the study of pectin by preparation of fragments representing all three major types of pectic polysaccharide: homogalacturonan (HG), rhamnogalacturonan-I (RG-I) and rhamnogalacturonan-II (RG-II). Such molecules have been synthesized by sequential coupling of building blocks, the so-called glycosyl donors (GD) and glycosyl acceptors (GA), which aimed at the formation of specific glycosidic linkages as they are present in the target oligosaccharides. Challenges in synthesis of pectic oligosaccharides are associated with often poor stereoselectivity of glycosylation reactions between GA and GD, in particular for the construction of 1,2-cis-glycosidic linkages, high degrees of branching of oligosaccharide chains of target molecules and the nature of many monosaccharide components of pectin, which are often acidic and sometimes rare branched-chain sugars. Preparation of carbohydrate building blocks, including de novo syntheses of unusual sugars, protecting group strategies for GA and GD, glycosylation methodologies and general strategies for oligosaccharide assembly are described with the focus on pectin fragments. Synthetic routes to fragments of each type of pectic polysaccharides are discussed in detail in separate sections and structures of all currently known synthetic pectin fragments are summarized. The unsolved problems and future prospects for improved access to synthetic pectin fragments are also discussed.
References
- Arabidopsis Genome Initiative (2000) Analysis of the genome sequence of the flowering plant Arabidopsis thaliana . Nature, 408, 796–815.
- Boons, G.J. (1998) Carbohydrate Chemistry. Blackie Academic, London.
- Buffet, M.A.J., Rich, J.R., McGavin, R.S., Reimer, K.B. (2004) Synthesis of a disaccharide fragment of rhamnogalacturonan II. Carbohydrate Research, 339, 2507–2513.
- Carpita, N., McCann, M. (2000) The cell wall. In: Biochemistry and Molecular Biology of Plants (eds B. Buchanan, W. Gruissem, and R.L. Jones), pp. 52–108. American Society of Plant Physiologists, Rockville, MD.
- Chauvin, A.L., Nepogodiev, S.A., Field, R.A. (2004) Synthesis of an apiose-containing disaccharide fragment of rhamnogalacturonan-II and some analogues. Carbohydrate Research, 339, 21–27.
- Chauvin, A.L., Nepogodiev, S.A., Field, R.A. (2005) Synthesis of a 2,3,4-triglycosylated rhamnoside fragment of rhamnogalacturonan-II side chain A using a late stage oxidation approach. Journal of Organic Chemistry, 70, 690–696.
- Clausen, M.H., Jorgensen, M.R., Thorsen, J., Madsen, R. (2001) A strategy for chemical synthesis of selectively methyl-esterified oligomers of galacturonic acid. Journal of the Chemical Society Perkin Transactions, 1, 543–551.
- Clausen, M.H., Madsen, R. (2003) Synthesis of hexasaccharide fragments of pectin. Chemistry – A European Journal, 9, 3821–3832.
-
Davis, N.J.,
Flitsch, S.L.
(1993)
Selective oxidation of monosaccharide derivatives to uronic acids.
Tetrahedron Letters,
34,
1181–1184.
10.1016/S0040-4039(00)77522-8 Google Scholar
- de Oliveira, M.T., Hughes, D.L., Nepogodiev, S.A., Field, R.A. (2008) Indirect approach to C-3 branched 1,2-cis-glycofuranosides: synthesis of aceric acid glycoside analogues. Carbohydrate Research, 343, 211–220.
-
Demchenko, A.V.
(2008)
Handbook of Chemical Glycosylation: Advances in Stereoselectivity and Therapeutic Relevance.
Wiley-VCH,
Weinheim.
10.1002/9783527621644 Google Scholar
- Deng, C.H., O'Neill, M.A., York, W.S. (2006) Selective chemical depolymerization of rhamnogalacturonans. Carbohydrate Research, 341, 474–484.
- Egelund, J., Petersen, B.L., Motawia, M.S., et al. (2006) Arabidopsis thaliana RGXT1 and RGXT2 encode Golgi-localized (1,3)-alpha-D-xylosyltransferases involved in the synthesis of pectic rhamnogalacturonan-II. Plant Cell, 18, 2593–2607.
- Ernst, B., Hart, G.W., Sinaÿ, P. (2000) Carbohydrates in Chemistry and Biology, Vol. 1. Wiley-VCH, Weinheim.
- Fan, H.N., Liu, M.Z., Lee, Y. (2002) Large-scale preparation of α-D-(1–4)-oligogalacturonic acids from pectic acid. Canadian Journal of Chemistry, 80, 900–903.
-
Fraser-Reid, B.,
Tatsuta, K.,
Thiem, J.
(2001)
Glycoscience: Chemistry and Chemical Biology, Vol.
2.
Springer-Verlag,
Berlin.
10.1007/978-3-662-11893-1 Google Scholar
- Grisebach, H., Schmid, R. (1972) Chemistry and biochemistry of branched-chain sugars. Angewandte Chemie International Edition, 11, 159–248.
- Guillaumie, F., Justesen, S.F.L., Mutenda, K.E., Roepstorff, P., Jensen, K.J., Thomas, O.R.T. (2006) Fractionation, solid-phase immobilization and chemical degradation of long pectin oligogalacturonides. Initial steps towards sequencing of oligosaccharides. Carbohydrate Research, 341, 118–129.
-
Hammerschmidt, F.,
Oehler, E.,
Polsterer, J.-P.,
Zbiral, E.,
Balzarini, J.,
DeClercq, E.
(1995)
A convenient route to D-apio-β-D-furanosyl- and 2′-deoxyapio-β-D-furanosyl nucleosides.
Liebigs Annalen
551–558.
10.1002/jlac.199519950375 Google Scholar
- Henrissat, B., Coutinho, P.M., Davies, G.J. (2001) A census of carbohydrate-active enzymes in the genome of Arabidopsis thaliana . Plant Molecular Biology, 47, 55–72.
- Hotchkiss, A.T., Hicks, K.B., Doner, L.W., Irwin, P.L. (1991) Isolation of oligogalacturonic acids in gram quantities by preparative HPLC. Carbohydrate Research, 215, 81–90.
- Hotchkiss, A.T., Lecrinier, S.L., Hicks, K.B. (2001) Isolation of oligogalacturonic acids up to DP 20 by preparative high-performance anion-exchange chromatography and pulsed amperometric detection. Carbohydrate Research, 334, 135–140.
- Jones, N.A., Nepogodiev, S.A., MacDonald, C.J., Hughes, D.L., Field, R.A. (2005) Synthesis of the branched-chain sugar aceric acid: A unique component of the pectic polysaccharide rhamnogalacturonan-II. Journal of Organic Chemistry, 70, 8556–8559.
- Khan, S.H., Hindsgaul, O. (1994) In: Molecular Glycobiology (eds. M. Fukuda, O. Hindsgaul), pp. 206–229. Oxford University Press, Oxford.
- Khan, S.H., O'Neill, R.A. (1996) Modern Methods in Carbohydrate Synthesis, Vol. 1. Harwood Academic, Amsterdam.
- Koóš, M., Micová, J., Steiner, B., Alföldi, J. (2002) An efficient and versatile synthesis of apiose and some C-1- aldehyde- and/or 2,3-O-protected derivatives. Tetrahedron Letters, 43, 5405–5406.
- Kramer, S., Nolting, B., Ott, A.J., Vogel, C. (2000) Synthesis of homogalacturonan fragments. Journal of Carbohydrate Chemistry, 19, 891–921.
- Magaud, D., Dolmazon, R., Anker, D., Doutheau, A., Dory, Y.L., Deslongchamps, P. (2000) Differential reactivity of α- and β-anomers of glycosyl accepters in glycosylations. A remote consequence of the endo-anomeric effect? Organic Letters, 2, 2275–2277.
- Magaud, D., Grandjean, C., Doutheau, A., et al. (1997) An efficient and highly stereoselective α(1–4) glycosylation between two D-galacturonic acid ester derivatives. Tetrahedron Letters, 38, 241–244.
- Magaud, D., Grandjean, C., Doutheau, A., et al. (1998) Synthesis of the two monomethyl esters of the disaccharide 4-O-α-D-galacturonosyl-D-galacturonic acid and of precursors for the preparation of higher oligomers methyl uronated in definite sequences. Carbohydrate Research, 314, 189–199.
- Maruyama, M., Takeda, T., Shimizu, N., Hada, N., Yamada, H. (2000) Synthesis of a model compound related to an anti-ulcer pectic polysaccharide. Carbohydrate Research, 325, 83–92.
- Merrifield, R.B. (1963) Solid phase peptide synthesis. 1. Synthesis of a tetrapeptide. Journal of the American Chemical Society, 85, 2149–2154.
- Mutter, M., Renard, C.M.G.C., Beldman, G., Schols, H.A., Voragen, A.G.J. (1998) Mode of action of RG-hydrolase and RG-lyase toward rhamnogalacturonan oligomers. Characterization of degradation products using RG-rhamnohydrolase and RG-galacturonohydrolase. Carbohydrate Research, 311, 155–164.
- Nakahara, Y., Ogawa, T. (1989) A highly stereocontrolled synthesis of the propyl glycoside of a decagalacturonic acid, a model-compound for the endogenous phytoalexin elicitor-active oligogalacturonic acids. Carbohydrate Research, 194, 95–114.
- Nakahara, Y., Ogawa, T. (1990a) Stereoselective total synthesis of dodecagalacturonic acid, a phytoalexin elicitor of soybean. Carbohydrate Research, 205, 147–159.
- Nakahara, Y., Ogawa, T. (1990b) Synthesis of (1–4)-linked galacturonic acid trisaccharides, a proposed plant wound-hormone and a stereoisomer Carbohydrate Research, 200, 363–375.
- Nepogodiev, S.A., Fais, M., Hughes, D.L., Field, R.A. (2008) Synthesis of a common trisaccharide fragment of side chain A and B of pectic polysaccharide rhamnogalacturonan-II. In preparation.
- Nepogodiev, S.A., Jones, N.A., Field, R.A. (2007) Plant cell wall glycans: Chemical synthesis of the branched sugar aceric acid. In: Frontiers in Modern Carbohydrate Chemistry (ed. A.V. Demchenko), pp. 34–49. American Chemical Society, Washington, DC.
- Nolting, B., Boye, H., Vogel, C. (2000) Synthesis of rhamnogalacturonan I fragments. Journal of Carbohydrate Chemistry, 19, 923–938.
- Nolting, B., Boye, H., Vogel, C. (2001) Block synthesis with galacturonate trichloroacetimidates. Journal of Carbohydrate Chemistry, 20, 585–610.
- O'Neill, M.A., Ishii, T., Albersheim, P., Darvill, A.G. (2004) Rhamnogalacturonan II: Structure and function of a borate cross-linked cell wall pectic polysaccharide. Annual Review of Plant Biology, 55, 109–139.
- Paulsen, H. (1982) Advances in selective chemical syntheses of complex oligosaccharides. Angewandte Chemie International Edition, 21, 155–173.
- Plante, O.J., Palmacci, E.R., Seeberger, P.H. (2001) Automated solid-phase synthesis of oligosaccharides. Science, 291, 1523–1527.
- Rao, Y., Boons, G.J. (2007) Highly convergent chemical synthesis of conformational epitopes of rhamnogalacturonan II. Angewandte Chemie International Edition, 46, 6148–6151.
- Rao, Y., Buskas, T., Albert, A., O'Neill, M.A., Hahn, M.G., Boons, G.J. (2008) Synthesis and immunological properties of a tetrasaccharide portion of the B side chain of rhamnogalacturonan II (RG-II). Chembiochem, 9, 381–388.
- Reiffarth, D., Reimer, K.B. (2008) Synthesis of two repeat units corresponding to the backbone of pectic polysaccharide rhamnogalacturonan I. Carbohydrate Research, 343, 179–188.
- Renard, C.M.G.C., Lahaye, M., Mutter, M., Voragen, F.G.J., Thibault, J.F. (1998) Isolation and structural characterisation of rhamnogalacturonan oligomers generated by controlled acid hydrolysis of sugar-beet pulp. Carbohydrate Research, 305, 271–280.
- Ridley, B.L., O'Neill, M.A., Mohnen, D.A. (2001) Pectins: structure, biosynthesis, and oligogalacturonide-related signaling. Phytochemistry, 57, 929–967.
- Rodríguez-Carvajal, M.A., Hervé du Penhoat, C., Mazeau, K., Doco, T., Pérez, S. (2003) The three-dimensional structure of the mega-oligosaccharide rhamnogalacturonan II monomer: a combined molecular modeling and NMR investigation. Carbohydrate Research, 338, 651–671.
- Scheller, H.V., Jensen, J.K., Sorensen, S.O., Harholt, J., Geshi, N. (2007) Biosynthesis of pectin. Physiologia Plantarum, 129, 283–295.
- Schols, H.A., Voragen, A.G.J., Colquhoun, I.J. (1994) Isolation and characterization of rhamnogalacturonan oligomers, liberated during degradation of pectic hairy regions by rhamnogalacturonase. Carbohydrate Research, 256, 97–111.
- Seeberger, P.H. (2008) Automated oligosaccharide synthesis. Chemical Society Reviews, 37, 19–28.
- Somerville, C., Bauer, S., Brininstool, G., et al. (2004) Toward a systems approach to understanding plant cell walls. Science, 306, 2206–2211.
- Spiro, M.D., Kates, K.A., Koller, A.L., O'Neill, M.A., Albersheim, P., Darvill, A.G. (1993) Purification and characterization of biologically-active 1,4-linked α-D-oligogalacturonides after partial digestion of polygalacturonic acid with endopolygalacturonase. Carbohydrate Research, 247, 9–20.
- Timmer, M.S.M., Stocker, B. Ch 4, L., Seeberger, P.H. (2006) De novo synthesis of aceric acid and an aceric acid building block. Journal of Organic Chemistry, 71, 8294–8297.
- Turnbull, J.E., Field, R.A. (2007) Emerging glycomics technologies. Nature Chemical Biology, 3, 74–77.
- van den Bos, L.J., Codee, J.D.C., Litjens, R.E.J.N., Dinkelaar, J., Overkleeft, H.S., van der Marel, G.A. (2007) Uronic acids in oligosaccharide synthesis. European Journal of Organic Chemistry 3963–3976.
- Vogel, C., Steffan, W., Ott, A.Y., Betaneli, V.I. (1992) D-Galacturonic acid derivatives as acceptors and donors in glycosylation reactions. Carbohydrate Research, 237, 115–129.
- Walbot, V. (2000) A green chapter in the book of life. Nature, 408, 794–795.
- Watson, R.R., Orenstein, N.S. (1975) Chemistry and biochemistry of apiose. Advances in Carbohydrate Chemistry and Biochemistry, 31, 135–184.
- Werz, D.B., Ranzinger, R., Herget, S., Adibekian, A., von der Lieth, C.W., Seeberger, P.H. (2007) Exploring the structural diversity of mammalian carbohydrates (‘Glycospace’) by statistical databank analysis. ACS Chemical Biology, 2, 685–691.
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