SYNTHESIS, CONFORMATIONAL-ANALYSIS, AND THE GLYCOSIDIC COUPLING REACTION OF SUBSTITUTED 2,7-DIOXABICYCLO[4.1.0]HEPTANES - 1,2-ANHYDRO-3,4-DI-O-BENZYL-BETA-L- AND BETA-D-RHAMNOPYRANOSES

1,2-Anhydro-3,4-di-O-benzyl-alpha-L-rhamnopyranose was synthesized from L-rhamnose, while the D-enantiomer was synthesized from methyl 6-deoxy-2,3-O-isopropylidene-alpha-D-mannopyranoside. For both of the syntheses, the key intermediates were 2-O-acetyl-3,4-di-O-benzyl-alpha-D- and -alpha-L-rhamnopyranosyl chlorides that were quantitatively prepared from the corresponding diacetates by chlorination. Ring closure of the chlorides was carried out readily with potassium tert-butoxide in oxolane, and crystalline 1,2-anhydro-3,4-di-O-benzyl-beta-D- and beta-L-rhamnopyranose were obtained in high yields. Conformational calculations, which were carried out using vicinal proton-proton coupling constants by the modified Karplus equation, suggested that the conformations of the pyranose rings of the title compounds were basically a half chair (H4(5)) with some flattening at C-4. Force-field calculations (MMP2) confirmed the experimental conformation with good agreement. The coupling reaction of the 1,2-anhydro-L-rhamnose ether with 1,2;3,4-di-O-isopropylidene-a-D-galactopyranose was effected in oxolane by catalysis by a Lewis acid, and only the alpha-linked disaccharide was obtained.