New Heterocyclic Derivatives of 2-Amino-1,6-anhydro-2-deoxy-β-D-glucopyranose Containing 1,4-Oxazepane or Azepane Ring

Abstract

Two heterocyclic derivatives of D-glucosamine, 2-amino-1,6-anhydro-2-deoxy-2-N,4-O-(ethane1,2-diyl)-β-D-glucopyranose (13) and 2-amino-1,6-anhydro-2,4-dideoxy-2-N,4-(propane-1,3-diyl)-β-D-glucopyranose (14) were prepared from 1,6-anhydro-β-D-glucopyranose (levoglucosan) in ten steps via O-4 or C-4 substituted 1,6:2,3-dianhydro-β-D-mannopyranose derivatives 2 and 4. Selective oxirane-ring cleavage with sodium azide at C-2 followed by tosylation afforded 2-azido-2-deoxy derivatives 7 and 8 of D-gluco configuration. These were reduced to amines and, after tosylation, azepane and oxazepane N-tosyl derivatives 11 and 12 were formed by intramolecular substitution. Their detosylation afforded the target D-glucosamine derivatives 13 and 14.