Synthesis of 3-hexuloses from 1,2:5,6-di-O-isopropylidenehexitols.
A simple, but low-yielding method for the synthesis of 3-hexuloses has been elaborated. Oxidation of 1,2:5,6-di-O-isopropylidenehexitols with bromine in the presence of barium carbonate, followed by mild-acid hydrolysis of the oxidation products gave the free hexuloses. Oxidation occurred at only one of the carbon atoms bearing free hydroxyl groups. From the D-mannitol derivative, D-arabino-3-hexulose was obtained via the di-O-isopropylidene derivative, whereas the D-glucitol derivative gave a mixture of the 1,2:5,6-di-O-isoprpylidene derivatives of L-xylo- and D-ribo-3-hexulose, separable by column chromatography. Mild-acid hydrolysis of the oxidation products afforded the free hexuloses.
Ekeberg
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D
Department of Chemistry and Biotechnology, Section Chemistry, Agricultural University of Norway, PO Box 5040, N-1432 As, Norway.
Morgenlie
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S
Stenstrøm
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Y
D001464:Barium / Q000737:chemistry; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000737:chemistry*; D001966:Bromine / Q000737:chemistry; D002254:Carbonates / Q000737:chemistry; D006601:Hexoses / Q000138:chemical synthesis*; D006868:Hydrolysis; D007661:Ketoses / Q000138:chemical synthesis*; D010084:Oxidation-Reduction; D013402:Sugar Alcohols / Q000737:chemistry*
D019086:Bridged Bicyclo Compounds, Heterocyclic; D002254:Carbonates; D006601:Hexoses; D007661:Ketoses; D013402:Sugar Alcohols; C441467:arabino-3-hexulose; C441469:ribo-3-hexulose; C441468:xylo-3-hexulose; D001464:Barium; C006685:barium carbonate; D001966:Bromine