| DOI | Resolve DOI: https://doi.org/10.1016/B978-0-12-746207-3.50017-6 |
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| Author | Search for: Perry, Malcolm B.1; Search for: Williams, David T.1 |
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| Affiliation | - National Research Council of Canada
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| Format | Text, Book Chapter |
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| Abstract | The synthesis of 3-deoxy-D-manno-octulosonic acid (KDO) (VIII) from D-mannose starts with the base catalyzed addition of nitromethane to D-mannose to give a mixture of l-deoxy-1-nitro-O-glycero-O-galactoheptitol (I) and l-deoxy-l-nitro-D-g/ycero-D-ta/o-heptitol (II). The acetylated crystalline I is boiled, in benzene solution, with sodium hydrogen carbonate to give crystalline pentaacetoxy-D-raafwo-l-nitro- 1-heptene (III) which is catalytically reduced to penta-0-acetyl-l,2-dideoxy-l-nitro-D-ma/i/to-heptitol (IV). Deacetylated IV is treated under modified Nef reaction conditions to yield 2-deoxy-D-raawzö-heptose (V). The 2-dœxy-O-manno-heptose is treated with aqueous sodium cyanide to yield a mixture of 3-deoxy-D-glycero-O-galacto-octonic acid (VI) and 3-deoxy-D-g/ycer0-D-ia/o-octonic acid (VII). The mixture of octonic acids (VI and VII) is smoothly oxidized with a modified vanadium chloride catalyst to give 3-deoxy-O-mannooctulosonic acid (VIII).
3-Deoxy-D-manno-octulosonic acid (VIII) [erroneously called 2-keto-3- deoxyoctonic acid (KDO) by some] was first detected by Levin and Racker and has since been shown to be a component of the lipopolysaccharides of gram-negative bacteria; it is considered that the so-called lipid A is joined through KD O to the "core" and polysaccharide portion of the molecule. The structure of KD O was established by Ghalambor and co-workers and was confirmed by the identification of 2-deoxy-D-manno-heptose as a degradation product and the identification of 3-dQOxy-O-glycero-O-galacto-octonic acid and 3-deoxy-O-glycero-O-talo-octomc acid as direct reduction products.
KDO has previously been made by the condensation of D-arabinose with oxaloacetic acid or di-/m-butyloxalacetic acid and by a route essentially the same as that described herein. |
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| Publication date | 1976 |
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| Publisher | ScienceDirect |
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| In | |
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| Series | |
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| Note | Authors were affiliated with the NRC Division of Biological Sciences at time of publication |
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| Language | English |
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| Peer reviewed | Yes |
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| NRC number | PERRY1976 |
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| NPARC number | 9369841 |
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| Export citation | Export as RIS |
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| Report a correction | Report a correction (opens in a new tab) |
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| Record identifier | 0ec81497-c362-4818-a3b5-97ec834271e5 |
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| Record created | 2009-07-10 |
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| Record modified | 2024-06-10 |
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