A GENERAL METHOD FOR THE SYNTHESIS OF CYCLODEXTRINYL ALDEHYDES AND CARBOXYLIC ACIDS

摘要

The selective synthesis of the primary-side monoaldehyde of beta-cyclodextrin, 6-deoxy-6-formyl-beta-cyclodextrin, was accomplished by oxidation of the corresponding tosylate utilizing the Nace reaction (DMSO/collidine). This monoaldehyde was then used as the starting material in several reactions including reduction, addition of NaHSO3, addition of the alpha-nucleophiles hydroxylamine and hydrazine, and reductive amination. Of particular interest is the conversion of the monoaldehyde to the primary side carboxylic acid, 6-deoxy-6-carboxy-beta-cyclodextrin, via bromine oxidation. This general method sequence can be applied to any tosyl derivative of cyclodextrin as demonstrated in the synthesis of beta-cyclodextrin-A,D-dialdehyde and beta-cyclodextrin-A,D-diacid. [References: 36]