Hexonic acids, 3-deoxy preparation

Deoxy-D-xy/o-hexonic acid (a-D-galactometasaccharinic acid, 111) can be prepared from D-galactose 289 the / -(d-lyxo) isomer can be isolated in smaller amounts from the mother liquors. 

H. B. Wood, Jr. and H. G. Fletcher, Jr., 2-Deoxy-D-ribose. VI. The preparation of derivatives of 3-deoxy-D-riAo-hexonic acid and 3-deoxy-D-araWno-hexonic acid therefrom. Some observations on the Kiliani synthesis, J. Org. Chem., 26 (1961) 1969-1973. 

Diethoxycarbonylallene, an active dienophile and ethoxycarbonylketen equivalent, has been used to prepare (83), which is a key intermediate for projected syntheses of antibiotic C-nucleosides. Treatment of such 2,3-dideoxyald-2-enonic acid esters as (84) with sodium methoxide yielded 3,6-anhydro-2-deoxy-hexonic acid esters [e.g. (85)] from an internal Michael reaction on the deacetylated derivative. ... 

A further study of the use of the Arndt-Eistert reaction in carbohydrate chemistry examined the reactions of the diazoketone (247) (prepared from a-D-glucoisosaccharinic acid), which gave mainly the orthoester (248) and both the ( )- and (Z)-isomers (249) of a 2,3-unsaturated methyl hexonate derivative on treatment with silver oxide in methanol. The 3-C-methylene derivative (248) is a useful precursor of 4-deoxy-3-C-methyl-D-hexoses. 

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