2-Deoxy-D-glucoside

A5. Arcos, M., and Lieberman, S., 5-Pregnene-3, 20a-diol-3-sulphate-20-(2 -acet-amido-2 -deoxy- ,D-glucoside) and 5-pregnene-3j8, 20a-diol-3, 20-disulphate. Two novel urinary conjugates. Biochemistry 6, 2032-2039 (1967). 

Studies have revealed that the deamination of 2-amino-2-deoxy-D-glucosides is more complicated than previously supposed. It has been reported that methyl 2-amino-2-deoxy-a- and -/3-d-glucopyranoside give, in addition to 2,5-anhydro-D-mannose, methyl 2-deoxy-2-C-formyl-a- and -/S-D-ribofuranoside (for example, 97 to 98) in yields of 25 and 19%, respectively, under the experi-... 

Dihydrooxadiazines can be made in related fashion and they too offer novel access to important products. For example, the (9-silylated D-glucal 70, irradiated at 350 nm in cyclohexane with dibenzyl azodicarboxylate, affords adduct 74 in 71% yield,74 and this with an acid catalyst can be used as a glycosylating agent to make /J-linked 2-amino-2-deoxy-D-glucosides.75 This chemistry also is applicable to furanoid glycals.74 Scheme 6 outlines the regio- and stereoselectivities of these cycloaddition reactions and their applications in synthetically useful processes. 

Acidic hydrolysis of 2-acylamino-2-deoxy-D-glucosides is incomplete, owing to the operation of two separate reaction-pathways, one leading to glycoside hydrolysis, the other to hydrolysis of the A-substituent. The product of the second reaction pathway is strongly resistant to further hy-... 

MeSiCls, TEA, THE, 60°C, 54-93% yield. The method was developed for the cleavage of 2-amino-2-deoxy-D-glucoside methoxycarbonyl derivatives. The acetate, PMB, Bn, Troc, acetonide and azide groups were stable to these conditions. 

Three papers have appeared on the isolation and purification of the 2-deoxy-D-glucoside-2-sulphamate sulphohydrolase (128) from liver174-176. The enzyme has been purified 40,000-fold utilizing four chromatographic steps. The purification procedures were followed using a specific substrate isolated from an acid hydrolysate of heparin. The subunit molecular weight (Mr) of the enzyme isolated from liver, kidney and placenta was assessed to be 56,000 using SDS/polyacrylamide-gel electrophoresis and the native enzyme results from the dimerisation of the subunits. 

Yonehara and coworkers isolated a-n-mannosyl 2-amino-2-deoxy- -D-glucoside (70), which is coproduced with a,o-trehalosamine by Strepto-... 

Aminohexyl ycopyranosides (D-galactoside, D-glucoside, D-fucoside, D-mannoside, D-xyloside, 2-acetamido-2-deoxy-D-glucoside)... 

L-lduronic acid glycosides are more readily hydrolysed by acid than the analogous neutral glycosides or the isomeric D-g /uco-acids, a difference that has been utilized in their isolation from glycosaminoglycans, e.g. heparin. Rate studies were carried out on several neutral and acidic glycosides and on 7V-acetyl-2-amino-2-deoxy-D-glucosides. ... 

Aqueous hydrolysis of a 3-(3-acetyI group in a 2-amino-2-deoxy-D-glucoside derivative is sixty times faster than that of ethyl acetate, evidently being catalyzed by the adjacent free 2-amino-group. ... 

A novel synthesis of 2-deoxy- -D-glucosides (54) (Scheme 11) has used Barton s Q-acylthiohydroxamate methodology, good 5-stereoselectivity being assured by the requirement that the 1-alkoxyglucos-l-yl radicals (55) generated by radical... 

Synthesis of amino-sugar glycosides is covered in Chapter 3, the formation of 2-acetamido-2-deoxy-D-glucosides from diazirines via glycosyl carbenes in Chapter 10, and the conversion of a deoxynojirimycin derivative into 2,6-dideoxy-2,6-imino-L-gulonic acid in Chapter 18. 

Phytosterols and their glucosides are common constituents of ferns. Acylated glucosides such as 820 (392) also occur in all ferns. From Pteris inaequalis var. aequata which contains 2-deoxy-D-glucose (835) abundantly, 2-deoxy-D-glucoside of P-sitosterol (821) has been isolated together with its P-D-glucoside (289). 

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