Carbohydrate Research 2000-07-24

Formation of unexpected substitution patterns in sulfonylbutylation of cyclomaltoheptaose promoted by host-guest interaction.

N Rogmann, J Seidel, P Mischnick

Index: Carbohydr. Res. 327(3) , 269-74, (2000)

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Abstract

The distribution of substituents in sulfonylbutylethers of cyclomaltoheptaose (beta-cyclodextrin) formed in aqueous medium has been determined by gas chromatography after hydrolysis and formation of the permethylated sulfonylfluoride derivatives. In contrast to other etherification reactions of beta-cyclodextrin, preferred substitution in position 3 of the glucose units has been detected. From 1H NMR and microcalorimetric experiments, the formation of host-guest complexes by beta-cyclodextrin and the reagent 1,4-butane sultone in water became evident. This spatial preorganization presumably favors the reaction with the O-3. In contrast, in methyl sulfoxide preferred 2-O-alkylation was obtained, indicating that host-guest interaction does not influence regioselectivity in this solvent.