Collect. Czech. Chem. Commun. 2005, 70, 1429-1446

Synthesis of 1,6-Anhydro-β-D-hexopyranoses Fused to the Piperidine 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 piperidine derivatives (6 and 17) containing fused 1,6-anhydro-β-D-hexopyranose moiety were prepared from 1,6-anhydro-β-D-glucopyranose (1). The first synthetic route led via the known 1,6:2,3-dianhydro-4-deoxy-4-(3-hydroxypropyl)-β-D-mannopyranose (2) obtained in four steps from 1. Its hydroxyl group was converted into amino group via tosylate and azide. The corresponding amino epoxide 5 readily rearranged into 3-amino-1,6-anhydro-3,4-dideoxy-3-N,4-C-(propane-1,3-diyl)-β-D-altropyranose (6). The second route used the known 1,6-anhydro-2,4-di-O-tosyl-β-D-ribo-hexopyranos-3-ulose (9) as an intermediate. Addition of allylmagnesium chloride to ketose 9 afforded 3-C-allyl-1,6-anhydro-2,4-di-O-tosyl-β-D-allopyranose (10). Hydroboration of its double bond followed by transformation of the resulting primary hydroxyl group into tosylamido group gave tritosyl derivative 15. Intramolecular replacement of the tosyloxy group in position 4 by tosylamido group gave tosylated piperidine derivative 16. Detosylation of 16 afforded the target 4-amino-1,6-anhydro-3,4-dideoxy-3-C,4-N-(propane-1,3-diyl)-β-D-gulopyranose (17).

Keywords: Carbohydrates; Heterocycles; 1,6-Anhydrosugars; Piperidines; Oxiranes; Alkaloids; Cyclizations; X-Ray diffraction; NMR spectroscopy; Conformation analysis.

References: 20 live references.