Synthesis and hydrolysis of aryl fluoroglycosides

Abstract

In this work, we have used a new approach for the synthesis of aryl fluoroglycoside analogues. This strategy used a simple metal-mediated anomeric arylation leading to phenolic fluoroglycosides. Moreover, we determined the rate constants of the acid-catalyzed hydrolysis of original and known mono- and polyfluorinated aryl O- and S-glycosides. For simple phenyl O-fluoroglucosides, the pseudo-first order rate constant for acid-catalyzed hydrolysis was smaller for the β anomer than for the α anomer. As for 4-carboxyphenyl O-galactosides, the rate constant varies as follows: nonfluorinated > 6-deoxy-6-fluoro > 3-deoxy-3-fluoro ≈ 4-deoxy-4-fluoro > 2-deoxy-2-fluoro > polyfluorinated. Finally, we observed a diminution in the hydrolysis rate constant with an increase in the number of integrated fluorine atoms as compared to the native carbohydrate.