Collect. Czech. Chem. Commun. 2000, 65, 1745-1753

Mitsunobu Transformations of 1,2-O-Isopropylidene-α-D-pentofuranoses Mediated by Zinc Salts

Jitka Moravcováa,*, Lucie Špilováa, Jindra Čapkováa, Florence Cheryb and Patrick Rollinb

a Department of Chemistry of Natural Compounds, Institute of Chemical Technology, Prague, Technická 5, 166 28 Prague 6, Czech Republic
b ICOA, Université d'Orléans, BP 6759, F-45067 Orléans Cedex 2, France


A one-pot regioselective heterofunctionalization of 1,2-O-isopropylidene-α-D-xylofuranose (1) and 1,2-O-isopropylidene-α-D-ribofuranose (2) with zinc azide, zinc thiocyanate or zinc N,N-dimethyldithiocarbamate via the Mitsunobu reaction has been performed. With 2, the reaction gave selectively the desired products substituted at C-5 in good isolated yields (60-65%). However, application of the same reaction conditions to 1 led to the predominant formation of a cyclic 3,5-anhydro derivative. In contrast, the reaction of hydrazoic acid with 1 afforded 5-azido-5-deoxy-1,2-O-isopropylidene-α-D-xylofuranose besides formerly unknown 5-azido-3,5-dideoxy-1,2-O-isopropylidene-α-D-glycero-pent-3-enofuranose and 3,5-diazido- 3,5-dideoxy-1,2-O-isopropylidene-α-D-ribofuranose; the yields depended on the reaction time and the molar ratio of reagents.

Keywords: Carbohydrates; Pentofuranoses; Mitsunobu reaction; Nucleophilic displacement; Zinc salts; Azidosugars; Anhydrosugars; Azides; Thiocyanates; Dithiocarbamates.

References: 28 live references.