Collect. Czech. Chem. Commun. 1984, 49, 433-443

Azido derivatives of 1,6-anhydro-β-D-hexopyranoses corresponding to 3-deoxy- and 4-deoxy-D-glucosamine

Ivan Černý, Tomáš Trnka and Miloslav Černý

Department of Organic Chemistry, Charles University, 128 40 Prague 2


Nucleophilic substitution of the tosyloxy group in 1,6-anhydro-3-deoxy-2-O-p-toluenesulfonyl-β-D-arabino-hexopyranose (II) with lithium azide gave derivative V which was acetolysed and deacetylated to 2-azido-2,3-dideoxy-D-ribo-hexose (IX). The oxirane ring in 1,6 : 2,3-dianhydro-4-deoxy-β-D-lyxo-hexopyranose (XII) was opened using lithium azide and the mixture of 2- and 3-azido derivatives XIII of D-xylo and XIV of D-arabino configuration formed was separated by an extraction procedure after previous selective trimethylsilylation. Azido derivative XIII was converted to 2-azido-2,4-dideoxy-D-xylo-hexose (XIX) on acetolysis and deacetylation. Hydrogenation of azido derivatives IX and XIX on palladium on charcoal and subsequent N-acetylation gave corresponding 3- and 4-deoxy derivatives of D-glucosamine, XI and XXI.