New Products from 1,5-Anhydro-D-fructose

1,5-Anhydro-D-fructose 1 (AF) is now available in larger amounts by enzymatic degradation of starch, and thus the utility of AF is the basis of the NEPSA project . A review covering the chemistry and biochemistry of AF has recently been published . In our ongoing research to use AF as a chiral starting material, we have focused our attention on modifying the unsaturated ketone 2 which is obtained in one step from AF. In order to create C-C bonds Michael conditions were applied to the unsaturated ketone 2 using carbon nucleophiles such as cyanide and diethylmalonate. The acetylated enolone 2a proved too sensitive to the basic reaction conditions resulting in hydrolysis or rearrangement (3, 4) depending on the solvent. Compound 4 is of interest as it is the acetylated version of Ascopyrone P which has been proven to possess antioxidant properties . The benzoylated ketone 2b was shown to be more stable towards the basic conditions and addition of diethylmalonate went smoothly to introduce the carbon substituent at C-4. The product isolated was the rearranged all-equatorial addition product 5. The reactions and their mechanisms will be discussed. Further manipulation of compound 5 is under investigation. EU-program : NEw Products from Starch derived Anhydro-D- fructose Andersen, S.; Lundt, I.; Marcussen, J.; Yu, S. Carb.Res. 2002, 337, 873-880 Andersen, S.; Isak, T.; Jensen, H. M.; Marcussen, J.; Yu, S. Anti-oxidant. PCT Int. Patent WO 0056838, 2000