Collect. Czech. Chem. Commun. 2005, 70, 466-478

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

Tomáš Trteka, Miloslav Černýa, Miloš Buděšínskýb,*, Tomáš Trnkaa and Ivana Císařovác

a Department of Organic Chemistry, Charles University, Hlavova 2030, 128 40 Prague 2, Czech Republic
b Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, 166 10 Prague 6, Czech Republic
c Department of Inorganic Chemistry , Charles University, Hlavova 2030, 128 40 Prague 2, Czech Republic


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.

Keywords: Carbohydrates; Aminosugars; Oxazepanes; Azepanes; Heterocycles; 1,6-Anhydrosugars; 2-Amino-2-deoxy-D-glucose; Oxiranes; Epoxides; Cyclizations; X-Ray diffraction; NMR spectroscopy; Conformation analysis.

References: 16 live references.