Synthesis of 3-deoxy-D-manno-octulosonic acid based on thioacetals

Yu. M. Mikshiev, B. B.Paidak, V. I. Kornilov, Yu. A. Zhdanov

Research Institute of Physics and Organic Chemistry, Rostov State University, Rostov-on-Don

Abstract: A new synthesis of 3-deoxy-D-manno-octulosonic acid (KDO) is developed interaction of 1,2-anhydro-3,4:5,6-di-O-isopropylidene-D-mannitol and glyoxalic acid ethyl-thioacetal on the presence of butyllithium yielded 2,2-bis(ethylthio)-2,3-dideoxy-5,6:7,8-di-O-isopropylidene-D-manno-octono-1,4-lactone.

Its deacetonation followed by acetylation and hydrolytic desulphurisation in the presence on N-bromosuccinimide led to 2-hydroxy-3-deoxy-5,6,7,8-tetra-O-acetyl-D-manno-2-octeno-1 ,4-lactone, which gave enolacetate upon acetylation.

Both lactones were transformed into (KDO) with high yields when treated with 3% trifluoroacetic acid; the product was identified as crystalline ammonium salt.

Russian Journal of Bioorganic Chemistry 1990, 16 (8):1118-1124

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