Aminodeoxy Derivatives

Amino sugars are components of antibiotic substances109 and bacterial polysaccharides,1,0 and are therefore of interest. The nucleoside antibiotics amicetin, bamicetin, and plicacetin contain, as the sugar residue, a monoaminopentadeoxy disaccharide that is closely related to maltose. In view of the reported antibiotic and antitumor properties of these pyrimidine nucleosides,111,112 the synthesis of aminodeoxy derivatives of maltose would be of interest. 

After hydrolysis of carboxyl-reduced and partially desulfated heparin with hydrochloric acid, Wolfrom and coworkers117 isolated a disaccharide that was identified118 as 2-amino-2-deoxy-4-0-a-D-glucopyran-osyl-D-glucopyranose ( maltosamine ) hydrochloride, which gave a crystalline N-acetyl derivative (50). This structure was subsequently 

Nucleophilic displacement of the sulfonate groups in methyl 2,6,2, 3, 4 -penta-0-acetyl-3,6 -di-0-(methylsulfonyl)-/3-maltoside was readily achieved with sodium azide in hexamethylphosphoric triamide, to give methyl 3-azido-4-0-(6-azido-6-deoxy-a-D-gluco-pyranosyl)-3-deoxy-/3-D-allopyranoside pentaacetate.45 Catalytic hydrogenation of the 3,6 -diazide, followed by acetylation, gave the 3,6 -diacetamido derivative in high, overall yield. In a similar sequence of reactions, methyl 2,3,2, 3, 4 -penta-0-acetyl-6,6 -di-0-p-tolylsulfonyl-/3-maltoside has been transformed into the corresponding 6,6 -diac-etamido derivative.45 

The potential importance of unsaturated sugars as synthetic and biological intermediates is widely recognized. It is therefore surprising that only two unsaturated maltose derivatives, hexa-O-ace-tylmaltal123,124 (51) and methyl 2,3,6-trideoxy-5-0-(2,3,4-tri-0-acetyl- 

Ethyl l-thio-/3-maltoside heptaaeetate (59) has proved to be a useful intermediate in the synthesis of the a-glycoside of maltose (see Section III).30 Treatment of /3-maltose octaacetate with ethanethiol and fused zinc chloride gave compound 59 in 83% yield. Synthesis of mal- 

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Should the compound treated with ammonia have an isolated, secondary sulfonyloxy group, the corresponding aminodeoxy derivative is... 

Of course, if the original molecule is not symmetrical, equimoleeular proportions of the two aminodeoxy derivatives will not result. Such conversions of sugars311 have been discussed324 by Stacey. An example is the preparation of methyl 3-amino-3-deoxy-j8-D-altroside (methyl epiglucosaminide ) in 40% yield from276 methyl 3,4,6-tri-O-acetyl-... 

The oximes of these glycosuloses are convenient starting-substances for the preparation of aminodeoxy derivatives of 1,6-anhydrohexopyra-noses455 their catalytic hydrogenation proceeds with a selectivity similar to that of the parent glycosuloses. 

Electrostatic printing Different cellulosics including aminodeoxy derivatives... 

Vol. 23, p. 158), and the use of imines and derivatives of D-serinal in similar reactions led to analogous 4- and 5-aminodeoxy derivatives. A synthesis of pyranoid enonolactones is mentioned in Chapter 13. 

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