2-amino-2-deoxy derivatives, preparation

This process (also known as the Ferrier II Reaction ) has proved to be of considerable value for the efficient, one-step conversion of 5,6-unsaturated hexopyranose derivatives into functionalized cyclohexanones useful for the preparation of such enantiomerically pure compounds as inositols and their amino, deoxy, unsaturated and selectively O-substituted derivatives, notably phosphate esters. In addition, the products of the carbocyclization have been incorporated into many complex compounds of interest in biological and medicinal chemistry. ... 

Methyl 6-amino-6-deoxy-a-D-glucopyranoside derivatives 2c were synthesized in our laboratory by a somewhat different procedure [31]. 6-0-Sulfonyl or 6-bromo-6-deoxy derivatives of methyl a-o-glucopyranoside were substituted at C-6 by sodium azide. The 6-azido-6-deoxy intermediate was then treated by acyl chlorides in the presence of triphenylphosphine (Staudinger reaction) to afford amido derivatives which were finally de-O-acetylated to give 2c. The same reaction pathway allowed the preparation of 6-alkylamido-6-deoxy-D-glucopy-ranose derivatives, starting from o-glucose [31]. 

I. Cerny, M. Budesinsky, T. Trnka, and M. Cerny, Preparation of 2-amino- 1,6-anhydro-2,3-dideoxy-jS-D-arabino-hexopyranose. H- and 13C-N.M.R. spectra of deoxy derivatives of 2-amino-l,6-anhydro-2-deoxy-D-glucose and 2-amino-l,6-anhydro-2-deoxy-D-mannose, Carbohydr. Res., 130 (1984) 103-114. 

J. Jary and K. Capek, Amino sugars. 5. Preparation of methyl-3,4-anhydro-6-deoxy-a-D-galactopyranoside derivatives, Collect. Czech. Chem. Commun., 31 (1966) 315-320. 

The amino nitrile synthesis is particularly useful for the preparation of 2-amino-2-deoxy derivatives of rare sugars which would be difficult to obtain as intermediates in a synthesis involving animation alone. Thus, 2-amino-2-deoxy-L-glucose and 2-amino-2-deoxy-L-mannose can be prepared in good yield from the readily available L-arabinose.11,18... 

The 2-azido-2-deoxy derivatives of mono- and disaccharides such as 27a and 27b are versatile intermediates in the preparation of 2-amino-2-deoxysaccharides23. 

Novel 2, 3 -deoxy fluorescent 3 -C-branched thymidine 5 -triphosphate analogues have been prepared and employed as potential terminators in DNA-sequencing reactions. The amino-nucleotide derivatives (105), (106) have been dye-labelled at the aliphatic amino-group with the oxazine dye JA242. ... 

A series of deoxy derivatives of butirosin A (162), including the 3 -deoxybutirosin A (163), 5"-amino-3, 5"-dideoxybutirosin (164), and 5"-amino-4, 5"-dideoxybutirosin A (165) were prepared by Woo et al. [84] via sequential deoxygenation of the corresponding trifluoromethylsulfonyl derivatives by nucleophilic substitution with sodium salt of thiophenol followed by reduction with sodium in liquid ammonia and... 

A series of 2"-amino-2"-deoxy and 2"-acylamido-2"-deoxy derivatives of 5-deoxy-5-epj-fluorodibekacin (compounds 292-298) were also prepared via an oxi-dation-methoxyimination-reduction sequence to introduce the 2"-NH2 group. All the new compoimds except 292 showed only limited or no antibacterial activity, and the cpt-amino derivative 293 exhibited much lower activity than 292 [147] (compounds 292 98). 

This method has also been employed for the preparation of 2-amino-2-deoxy derivatives of levoglucosan (see Sect. VI,1,a). 

Ammonolysis of l,6 3,4-dianhydro-2-0-benzyl-/3-D-galactopyran-ose (188) affords the 4-amino-4-deoxy derivative.740 It was also used for the preparation of the 2-amino-4-fluoro- and 4-amino-2-fluoro-2,4-dideoxy derivatives of l,6-anhydro-/3-D-glucopyranose.381 The oxirane ring of most dianhydrides is readily split not only by ammonia but also by its derivatives, such as methylamine, dimethylamine,320,7 7 and benzylamine.635... 

The cyclic acetals have been of great assistance in the preparation of, for example, methylated sugars, - deoxy sugars, and amino-deoxy sugars. The specific syntheses of many di- and tri-saccharides have been described - in these, a suitable acetal of the aldose is caused to react with a poly-O-acetylglycosyl halide or a bromo- or chloro-hydrin derivative. 

Cyclic AMP (cAMP) has continued to attract considerable attention during the past year. 5 -Amino-5 -deoxy-derivatives (16) and the ara.-analogue (17) of cAMP have been prepared but their biochemical... 

A. Yamamoto, C. Miyashita, and H. Tsukamoto, Amino sugars. I. Preparation of Y-acyl derivatives of 2-acetamido-2-deoxy-P-D-glucosylamine, Chem. Pharm. Bull, 13 (1965) 1036-1041. 

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