Synthesis of plant arabinogalactans

Abstract

Plant arabinogalactans consisting of a b-(1®6)-linked D-galactopyranosyl oligosaccharide backbone with a-(1®2)-L-arabinofuranosyl branches are synthesized based on the 1,2-anhydro galactopyranose technique, orthogonal (methoxydimethyl)methyl (MIP) and (2-naphthyl)methyl (NAP) protection strategy, and selective acylation or glycosylation method. The third method is the most simple and effective and it is also used for the synthesis of arabinogalactans composed of a b-(1®6)-linked D-galactopyranosyl oligosaccharide backbone with a-(1®3)-L-arabinofuranosyl branches.

Keywords

arabinogalactan / oligosaccharide synthesis

References

[1] Bertozzi C R, Kiessling L L. Chemical glycobiology. Science, 2001, 291: 2357-2364

[2] Kong F. Regio- and stereoselective synthesis of oligosaccharides with unprotected or lightly protected sugars as glycosyl acceptors. Curr Org Chem, 2003, 7(9): 841-865

[3] Davis B G. Recent development in oligosaccharide synthesis, J Chem Soc Perkin Trans 1, 2000, (14): 2137-2160

[4] Schmidt R R, Kinzy W. Adv Carbohydr Chem Biochem, 1994, 50: 21-125

[5] Toshima K, Tatsuta K. Recent progress in O-glycosylation methods and its application to natural products synthesis. Chem Rev, 1993, 93: 1503-1531

[6] Clarke A E, Anderson R L, Stone B A. Form and function of arabinogalactans and arabinogalactan-protein. Phytochemistry, 1979, 18: 521-528

[7] Yamada H, Kiyohara H, Cyong J C, Otsuka Y. Studies on polysaccharides from Angelica acutiloba-IV, characterization of anti-complementary arabinogalactan from the roots of Angelica acutiloba Kitagawa. Mol Immunol, 1985, 22: 295-304

[8] Kiyohara H, Yamada H, Cyong J C, Otsuka Y. Characterization and function of arabinogalactans. J Pharmacobio-Dyn, 1986, 9: 339-346

[9] Shimizu N, Tomoda M, Gonda R. Studies on the constituents of edible and medicinal plants. Chem Pharm Bull (Tokyo), 1989, 37: 1329-1332

[10] Egert D, Beuscher N. Studies on antigen specificity of immunoreactive arabinogalactan proteins extracted from Baptisa tinctoria and Echinacea purpurea. Planta Med, 1992, 58: 163-165

[11] Hoson T. Structure and function of plant cell walls: immunological approaches. Int Rev Cytol, 1991, 130: 233-268

[12] Steffan W, Kovac P, Albersheim P, Darvill A G, Hahn M G. Characterization of a monoclonal antibody that recognizes an arabinosylated β-1-6-galactan epitope in plant complex carbohydrates. Carbohydr Res, 1995, 275: 295-307

[13] Timmers C M, Wigchert S C M, Leeuwenburgh M A, van der Marel G A, van Boom J H. Synthesis of tetrameric arabinogalactans based on 1,2-anhydrosugars. Eur J Org Chem, 1998, 1: 91-97

[14] Borbás A, Jánossy L, Lipták A. Scope and limitation of the application of the (methoxydimethyl)methyl group in the synthesis of 2'-O-, 6'-O- and 2',6'-di-O-(α-L-arabinofuranosyl)-β-D-galactopyranosyl-(1→6)-D-galactoses. Carbohydr Res, 1999, 318: 98-109

[15] Csávás M, Borbás A, Jánossy L, Batta G, Lipták A. Synthesis of the α-L-Araf-(1→2)-β-D-Galp-(1→6)-β-D-Galp-(1→6)-[α-L-Araf-(1→2)]-β-D-Galp-(1→6)-D-Gal hexasaccharide as a possible repeating unit of the cell-cultured exudates of Echinacea purpurea arabinogalactan. Carbohydr Res, 2001, 336: 107-115

[16] Csávás M, Borbás A, Szilagyi L, Lipták A. Successful combination of (methoxydimethyl)methyl (MIP) and (2-naphthyl)methyl (NAP) ethers for the synthesis of arabinogalactan-type oligosaccharides. Synlett, 2002, 6: 887-890

[17] Csávás M, Borbás A, Jánossy L, Lipták A. Synthesis of an arabinogalactan-type octa- abd two isomeric nonasaccharides. Suitable tuning of protecting groups. Tetrahedron Lett, 2003, 44: 631-635

[18] Du Y, Pan Q, Kong F. Synthesis of a tetrasaccharide representing minimal epitope of arabinogalactan. Carbohydr Res, 2000, 323: 28-35

[19] Du Y, Pan Q, Kong F. Synthesis of 3-O-arabinosylated (1-6)-galactan. J Carbohydr Chem, 2001, 20: 297-306

[20] Ning J, Yi Y, Yao Z. An efficient method for the synthesis of 2,6-branched galacto-oligosaccharides and its application to the synthesis of three tetrasaccharides and a hexasaccharide related to the arabinogalactans (AGs). Synlett 2003, 14: 2208-2212

[21] Zeng Y, Li A, Kong F. A concise synthesis of arabinogalactan with β-(1→6) galactopyranose backbone and α-(1→2) arabinofuranose side chains. Tetrahedron Lett, 2003, 44: 8325-8329

[22] Li A, Zeng Y, Kong, F. An effective synthesis of arabinogalactan with β-(1→6) galactopyranose backbone and α-(1→2) arabinofuranose side chains. Carbohydr Res, 2004, 339: 673-681

[23] Gu G, Du Y, Kong, F. Synthesis of a hexasaccharide that relates to the arabinogalactan epitope. Carbohydr Res, 2001, 336: 99-106

[24] Li A, Kong F. Concise syntheses of arabinogalactans consisting of β-(1→6)-linked galactopyranosyl backbone and α-(1→3)-linked arabinofuranosyl side chains. Chin J Chem, 2005, 23: 7-10

[25] Li A, Kong, F. Syntheses of arabinogalactans consisting of β-(1→6)-linked D-galactopyranosyl backbone and α-(1→3)-linked L-arabinofuranosyl side chains. Carbohydr Res, 2004, 339: 1847-1856

[26] Li A, Kong, F. Concise syntheses of arabinogalactans with β-(1→6)-linked galactopyranose backbones and α-(1→3)- and α-(1→2)-linked arabinofuranose side chains. Biorg Med Chem, 2005, 13: 839-853

[27] Lipták A, Fugedi P, Kerekgyarto J, Nanasi P. Preparation of mixed-acetal derivatives of carbohydrates by acetal-exchange reaction. Carbohydr Res, 1983, 113: 225-231

[28] Gaunt M J, Yu J, Spencer J B. Rational design of benzyl-type protecting groups allows sequential deprotection of hydroxyl groups by catalytic hydrogenolysis. J Org Chem, 1998, 63: 4172-4173

[29] Wang W, Kong F. New method for regio- and stereoselective synthesis of oligosaccharides. J Org Chem, 1998, 63: 5744-5745

[30] Wang W, Kong F. A highly convergent synthesis of the elicitor hexasaccharide. Tetrahedron Lett, 1998, 39: 1937-1940

[31] Wang W, Kong F. Regio- and steroselective synthesis of mannose-containing oligosaccharides. Angew Chem Int Ed, 1999, 38: 1247-1250

[32] Kong F. Recent studies on reaction pathways and applications of sugar orthoresters in synthesis of oligosaccharides. Carbohydr Res, 2007, 342: 345-373

[33] Byramova N E, Ovchinnikov M V, Backinowsky L V, Kochetkov N K. Selective removal of O-acetyl groups in the presence of O-benzoyl groups by acid-catalyzed methanolysis. Carbohydr Res, 1983, 124: c8-c11

[34] Du Y, Pan Q, Kong F. Regio- and steroselective synthesis of 1-5-linked arabinofuranosyl oligosaccharides using unprotected furanoside donors. Synlett, 1999:, 1648-1652

[35] Du Y, Pan Q, Kong, F. A facile synthesis of 1-5-linked arabinofuranosyl oligosaccharides. Carbohydr Res, 2000, 329: 17-24

[36] Ding X, Wang W, Kong F. Selective O-detritylation of sugar derivatives. Carbohydr Res, 1997, 303: 445-448

[37] Du Y, Zhang M, Kong F. Concise synthesis of 3,6-branched oligosaccharides. Org Lett, 2000, 2: 3797-3800

[38] Du Y, Zhang M, Kong F. Facile synthesis biologically important pentasaccharides. Tetrahedron, 2001, 57: 1757-1763

[39] Kong F, Lu D, Zhou S. Synthesis and conformation of 1,3-anhydro-2,4,6-tri-O-benzyl-D-galactose. Carbohydr Res, 1990, 198: 141-147

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