Deoxysugars via microbial reduction of 5-acyl-isoxazolines: application to the synthesis of 3-deoxy-D-fructose and derivatives.
5-Acylisoxazolines 3a-d were obtained by 1,3-dipolar cycloaddition from acetoxymethyl vinyl ketone and nitro precursors. Compounds 3a-d were biotransformed by Aspergillus niger into a 1:1 mixture of stereomers of 5-dihydroxyethyl isoxazolines (+)-4a-d (anti) and (-)-5a-d (syn). Both stereomers were obtained in good yields and with high optical purities. Carbonyl reduction by Aspergillus niger produces alcohols of R-configuration thus giving an access to D-sugar analogues: Compound (+)-4d was converted to 3-deoxy-D-erythro-hexulose and several protected derivatives. Total synthesis of 3-deoxy-D-fructose-6-phosphate was also achieved in two steps and 64% overall yield from (+)-4d.
Université Blaise Pascal, Laboratoire SEESIB, UMR 6504, 63177 Aubière Cedex, France. gefflaut@chimtp.univ-bpclermont.fr
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Gefflaut
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Martin
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Delor
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Besse
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Veschambre
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Bolte
D000107:Acetylation; D001234:Aspergillus niger / Q000378:metabolism*; D001711:Biotransformation; D003837:Deoxy Sugars / Q000096:biosynthesis*; D007555:Isoxazoles / Q000378:metabolism*; D007661:Ketoses / Q000096:biosynthesis*; D010084:Oxidation-Reduction; D013237:Stereoisomerism
D003837:Deoxy Sugars; D007555:Isoxazoles; D007661:Ketoses; C068286:3-deoxyhexulose