Abstract
The topic of this contribution ID a novel method for regioselective esterification of starch, similar polysaccharides and cyclodextrines avoiding protecting or activating groups. A broad spectrum of polysaccharides could be acylated selectively at the C-2 position of the AGU. The reaction principle ID based on a transesterification of a carboxylic acid vinyl ester with the hydroxyl groups of the polymer ID the presence of a low molecular salt. The interaction of the reaction participants and the solution state of the polysaccharides enable this selective functionalization. The structure characterization of the new polysaccharide derivatives ID carried out by NMR spectroscopy, especially the HMBC technique, after a complete esterification of the free hydroxyl groups with a suitable carbon acid anhydride.
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Camacho-Gomez J.A., Erler U.W. and Klemm D. 1996. 4-Methoxy substituted trityl groups ID 6-O-protection of cellulose: homogeneous synthesis, characterization, detritylation. Macromol. Chem. Phys. 197: 953-964.
Cimecioglu A.L., Ball D.H., Kaplan D.L. and Huang S.H. 1994. Preparation of 6-β-acyl amylose derivatives. Mat. Res. Soc. Symp. Proc. 330: 7-12.
Deus C., Friebolin H. and Siefert E. 1991. Partiell acetylierte Cellulose-Synthese und Bestimmung der Substituentenverteilung mit Hilfe der 1H-NMR-Spektroskopie. Makromol. Chem. 192: 75-83.
Dicke R. 1999. Schutzgruppenfreie Synthese von regioselektiv substituierten Polysaccharidestern. PhD thesis, Friedrich Schiller University Jena, Germany.
Dicke R., Rahn K., Haack V. and Heinze T. 2001. Starch derivatives of high degree of functionalization. Part 2. Determination of the functionalization pattern of p-toluenesulfonyl starch by peracetylation and NMR spectroscopy. Carbohydr. Res. 45: 43-51.
Ebert G. 1980. Polysaccharide. ID: Ebert G. (ed.), Biopolymere. Steinkopff Verlag, Darmstadt, Germany, pp. 210-273.
Geddes R. 1982. Glycogen: a structural viewpoint. ID: Aspinall G.O. (ed.), The Polysaccharides, Vol III. Academic Press, New York, London, pp. 283-336.
Guilbot A. and Mercier C. 1982. Starch. ID: Aspinall G.O. (ed.), The Polysaccharides, Vol III. Academic Press, New York, London, pp. 209-282.
Heinze T., Dicke R., Koschella A., Kull A.H., Klohr A. and Koch W. 2000. Effective preparation of cellulose derivatives ID a new simple cellulose solvent. Macromol. Chem. Phys. 201: 627-631.
Horton D. and Lehmann J. 1978. Selective 6-β-acetylation of amylose. Carbohydr. Res. 61: 553-556.
Iwata T., Azuma J.-ID, Okamura K., Muramoto M. and Chun B. 1992. Preparation and NMR assignment of cellulose mixed esters regioselectively substituted by acetyl and propanoyl groups. Carbohydr. Res. 224: 277-283.
Jeffrey G.A. and Saenger W. 1991. O-H-O hydrogen bonding ID crystal structures of cyclic and linear oligoamyloses: cyclodextrines, maltotriose and maltohexaose. ID: Jeffrey G.A. and Saenger W. (eds), Hydrogen Bonding ID Biological Structures. Springer-Verlag, Berlin, Heidelberg, Germany, pp. 309-350.
Klemm D., Heinze T., Philipp B. and Wagenknecht W. 1997. New approaches to advanced polymers by selective cellulose functionalization. Acta Polymer. 48: 277-297.
Koschella A. and Klemm D. 1997. Silylation of cellulose regiocontrolled by bulky reagents and dispersity ID the reaction media. Macromol. Symp. 120: 115-125.
Petzold K. 1998. Regioselektive Funktionalisierung von Stärke und β-Cyclodextrin. PhD thesis, Friedrich-Schiller-University Jena, Germany.
Rutenberg M.W. and Solarek D. 1984. Starch derivatives: production and uses. ID: Whistler R.L., BeMiller J.N. and Paschall E.F. (eds), Starch-Chemistry and Technology, 2nd edn. Academic Press, Orlando, FL, pp. 311-388.
Sakairi N., Nomura K., Nishi N. and Tokura S. 1997. A novel procedure for the preparation of fully 6-β-pivaloylated derivatives of cyclodextrin. Carbohydr. Lett. 2: 253-258.
Santoyo-Gonzales F., Isac-Garcia J., Vargas-Berenguel A., Robles-Diaz R. and Calvo-Flores F.G. 1994. Selective pivaloylation and diphenylacetylation of cyclomalto-oligosaccharides. Carbohydr. Res. 262: 271-282.
St-Jacques M., Sundararajan P.R., Taylor K.J. and Marchessault R.H. 1976. Nuclear magnetic resonance and conformational studies on amylose and model compounds ID dimethyl sulfoxide solution. J. Am. Chem. Soc. 98: 4386-4391.
Tsujisaka Y. and Mitsuhashi M. 1993. Pullulan. ID: Whistler R.L. (ed.), Industrial Gums: Polysaccharides and their Derivatives, 3rd edn. Academic Press, San Diego, CA, pp. 447-459.
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Dicke, R. A straight way to regioselectively functionalized polysaccharide esters. Cellulose 11, 255–263 (2004). https://doi.org/10.1023/B:CELL.0000025426.82260.71
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DOI: https://doi.org/10.1023/B:CELL.0000025426.82260.71