A Convenient Synthesis of 3-Deoxy-D-gluco-2-octulosonate (D-gluco-KDO) |
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Authors: | Dominique Lafont Monika Hoch Richard R Schmidt |
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Institution: | 1. Fakult?t Chemie, Universit?t Konstanz , Postfach 556O, D-7750 , Konstanz , Germany;2. Laboratoire de Chimie Organique 2 , Université Claude-Bernard Lyon 1 , E. S. C. I. L., 43, Boulevard du 11-Novembre-1918, 69622 , Villeurbanne Cedex , France;3. Fakult?t Chemie, Universit?t Konstanz , Postfach 556O, D-7750 , Konstanz , Germany |
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Abstract: | β-Lithiated acrylates have proven to be versatile pyruvate β-carbanion equivalents which are also useful in D-manno-KDO synthesis. The secondary amine adducts of acetylenedicarboxylate 4 display the same versatility, as demonstrated in this paper. However, on reaction with 2,3:4, 5-di-O-isopropylidene-D-arabinose 6, the diastereofacial selectivity is in favor of the gluco-isomer, thus leading with lithiated compounds 4A, preferentially to α-aminobutenolides 7-(g). The best results were obtained with the morpholine adduct of di-tert.-butyl acetylenedicarboxylate 4d which afforded the gluco-isomer 7d-(g) as an easily separable crystalline material. Its deamination and concomitant deisopropylidenation with trifluoroacetic acid provided the known α-hydroxy-butenolide 8b-(g), which was transformed via decarboxylation product 9-(g) to D-gluco-KDO 10-(g) thus concluding a convert four step synthesis of this compound via crystalline intermediates. |
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