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This work reports a modular and rapid approach to the stereoselective synthesis of a variety of α- and β-(1→2)-linked C-disaccharides. The key step is a Ni-catalyzed cross-coupling reaction of D-glucal pinacol boronate with alkyl halide glycoside easily prepared from commercially available D-glucal. The products of this sp(2) -sp(3) cross-coupling reaction can be converted to glucopyranosyl, mannopyranosyl, or 2-deoxy-glucopyranosyl C-mannopyranosides by one- or two-step stereoselective oxidative-reductive transformations. To the best of our knowledge, we demonstrated the first synthetic application of a challenging sp(2) -sp(3) Suzuki-Miyaura cross-coupling reaction in carbohydrate chemistry.

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A recently described bangle lectin (PHL) from the bacterium Photorhabdus asymbiotica was identified as a mainly fucose-binding protein that could play an important role in the host-pathogen interaction and in the modulation of host immune response. Structural studies showed that PHL is a homo-dimer that contains up to seven l-fucose-specific binding sites per monomer. For these reasons, potential ligands of the PHL lectin: α-l-fucopyranosyl-containing mono-, di-, tetra-, hexa- and dodecavalent ligands were tested. Two types of polyvalent structures were investigated – calix[4]arenes and dendrimers. The shared feature of all these structures was a C-glycosidic bond instead of the more common but physiologically unstable O-glycosidic bond. The inhibition potential of the tested structures was assessed using different techniques – hemagglutination, surface plasmon resonance, isothermal titration calorimetry, and cell cross-linking. All the ligands proved to be better than free l-fucose. The most active hexavalent dendrimer exhibited affinity three orders of magnitude higher than that of standard l-fucose. To determine the binding mode of some ligands, crystal complex PHL/fucosides 2 – 4 were prepared and studied using X-ray crystallography. The electron density in complexes proved the presence of the compounds in 6 out of 7 fucose-binding sites.

Suzuki-Miyaura Reaction. -The key step comprises a Ni-catalyzed cross-coupling reaction of D-glucal pinacol boronate with alkylbromide or alkyliodide glycoside, thus representing the first example for a challenging sp 2 -sp 3 cross-coupling in carbohydrate chemistry. -(OROSZOVA, B.; CHOUTKA, J.; POHL, R.; PARKAN*, K.; Chem. -Eur. J. 21 (2015) 19, 7043-7047, http://dx.