Wiley InterScience Backfile Collection 1832-2000
Chemistry and Pharmacology
---Electroreducible amphiphilic aromatic ketones derived from D-glucose and D-glucofuranurono-6,3-lactone (D-glucurone) have been synthesized by Schmidt condensation and reaction of the unprotected lactone with the appropriate substrates, respectively. The macroscale electrolyses of the glucose derivatives, performed in an aprotic solvent (DMF), yield the pinacols possessing two glycosidic side chains. Under the same conditions of electrolysis with the D-glucurone derivative, the glyosidic carbon-oxygen bond is cleaved. The use of a redox mediator (couple anthracene-•/anthracene) has demonstrated that a glucosidic bond can be reduced by a homogeneous electron transfer. In the presence of a proton donor the expected D-glucuronic pinacol is obtained. The radical-radical coupling involves the formation of two chiral centers. The diastereo- and the enantioselectivity of the reaction have been studied by 1H- and 2H-NMR spectroscopy, respectively.
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