Altrose oxidation

Alloslde, methyl 2-acetamido-2-deoxy-a-D-, derivatives, 202 —, methyl 2,3-anhydro-4,6-0-benzyli-dene-a-D-, 51, 227 Altraric acid, 2,5-anhydro-n-, 55 Altronic acid, 2-amino-2-deoxy-n-, 54 —, 2,5-anhydro-D-, 55 Altropyranoside, methyl 3-amino-3-deoxy- 8-D-, 50 Altrose, oxidation of, 15 —, 2-amino-2-deoxy-D-, methyl ethers of, 202, 214... 

Answer Beginning with D-ribose, a Kiliani-Fischer synthesis gives allose and altrose. Oxidation D-allose with nitric acid gives the optically inactive product aldaric acid. Oxidation of D-altrose with nitric acid gives optically active altraric acid. 

Problem 22.57 (a) Write shorthand open structures for a ketohexose (I) and an aldohexose (II) which form the same osazone as D-(-)-altrose (III), the C epimer of o-mannose, and for the aric acid (IV) formed by HNOj oxidation of the o-aldohexoses (III) and o-talose (V). (b) Write shorthand and conformational structures for -D-altropyranose (VI). ... 

Mycaminose has been found as a component of carbomycin (Magna-mycin)83 and, structurally, it resembles desosamine84 (see Table II). On periodate oxidation, one carbon atom is split out, to yield a seven-carbon amino sugar the results of subsequent reaction with the oxidant indicated the presence of a hydroxyl group at C4. Alkaline deamination of the seven-carbon sugar proceeded at a rate similar to that of 2-amino-2-deoxy-D-glucose, whereas mycaminose itself reacted far more rapidly this indicates the dimethylamino group to be at C3. Mycaminose is believed to be 3,6-dideoxy-3-dimethylamino-/3-D-altrose.84a... 

The structure of celtrobiose was established through its oxidation to celtrobionic acid and subsequent cleavage with N sulfuric acid to d-glucose and n-altronic acid. Since the biose linkage should not be affected by the aluminum chloride rearrangement, celtrobiose was thus proved to be 4-j8-D-glucopyranosido-D-altrose. 

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