161970-47-4Relevant articles and documents
Stereospecific molybdic acid-catalyzed isomerization of 2-hexuloses to branched-chain aldoses
Hricoviniova-Bilikova, Zuzana,Hricovini, Milos,Petrusova, Maria,Serianni, Anthony S.,Petrus, Ladislav
, p. 38 - 46 (1999)
On treatment with a catalytic amount of molybdic acid in aqueous solution, the 2-ketohexoses D-fructose, L-sorbose and D-tagatose undergo a stereospecific intramolecular rearrangement to give the corresponding 2-C-(hydroxymethyl)aldoses, 2-C-(hydroxymethyl)-D-ribose (D-hamamelose), 2-C-(hydroxymethyl)-L-lyxose, and 2-C-(hydroxymethyl)-D-xylose, respectively. At equilibrium, the ratio of 2-ketose to 2-C-(hydroxymethyl)aldose ranged from 14:1 (fructose) to 32:1 (sorbose). A similar treatment of D-psicose failed to yield a significant amount of the corresponding branched-chain aldose. The equilibria can be shifted with the addition of boric acid to the reaction mixture; under these conditions, ratios of 3:1 and 7:1 were obserwed for D-fructose and L-sorbose, respectively. A mechanistic study with D-(3-13C)fructose afforded D-(1-13C)hamamelose, thus confirming C-3 - C-4 bond cleavage with concomitant C-2 - C-3 transposition suggested from recent studies with D-(2-13C)fructose. Copyright (C) 1999 Elsevier Science Ltd.
