Glycosylamines and Glycosylammonium Salts

1 Glycosylamines and Glycosylammonium Salts. - X-Ray crystallography has shown that iV-phenyl-, iV-4-chlorophenyl- and iV-carboxamido-D-man-nosylamine are in the P-pyranosyl form in the solid state, whereas mannose oxime is in the open chain form. The conclusion from an examination of the conformations of various 2,3,4,6-tetra-O-acetyl-iV-aryl-D-glucopyanosylamines in neutral and protonated form was that there was no evidence to support the existence of a reverse anomeric effect.  

A 27-step synthesis of spicamycin amino-nucleoside (1) from myo-inositol featured a palladium-catalysed coupling of 5-chloropurine and with a glycosylamine derivative. Full details have been published on the products obtained from reactions of 5,6-diamino-2-methoxy-3-methylpyrimidi iV-4(3H)-one with xylose and with other pentoses in alcohol solutions (cf. Vol. 27, p. 127, ref. 8).  

The flavin ribosides 2, required asprobes of the pairing properties of flavin-containing oligonucleotides, were synthesized by elaboration of the corresponding JV-(2-nitro-4,5-dimethylphenyl)-riboside triacetates. The 0-deprotected 

Carbohydrate Chemistry, Volume 34 The Royal Society of Chemistry, 2003 

Several 4-thio-D-glucofuranosylamine disaccharide derivatives such as 8 (a p, 1 3) were obtained by direct condensation of 4-thio-D-glucose with an amino-sugar. A review of the application of palladium si-allyl complexes of unsaturated carbohydrates in fuctionalization at the anomeric centre included the use of 7V-nucleophiles to provide unsaturated JV-glycosyl derivatives. Cyclic l,2-iV,0-phosphate derivatives of aldoses feature as intermediates in selective 2-0-phosphorylation reactions (see Chapter 7). 

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