Highly efficient removal of allyloxycarbonyl(Alloc)function provides a practical orthogonal protective strategy for carbohydrates

Highly efficient removal of allyloxycarbonyl （Alloc） group was achieved in the presence of CH3COONH4, Pd[P（C6H5）3]4, and NaBH4 in MeOH-THF, within 5 min in almost quantitative yields （〉90%, isolated yield） without affecting acetyl, benzoyl, isopropylidene, benzylidene, allyl, benzyl, benzyl carbonate, or azido groups.

Chemical synthesis of a synthetically useful L-galactosaminuronic acid building block

Most bacterial cell surface glycans are structurally unique, and have been considered as ideal target molecules for the developments of detection and diagnosis techniques, as well as vaccines. Chemical synthesis has been a promising approach to prepare well-defined oligosaccharides, facilitating the structure-activity relationship exploration and biomedical applications of bacterial glycans. L-Galactosaminuronic acid is a rare sugar that has been only found in cell surface glycans of gram-negative bacteria. Here, an orthogonally protected L-galactosaminuronic acid building block was designed and chemically synthesized. A synthetic strategy based on glycal addition and TEMPO/BAIB-mediated C6 oxidation served well for the transformation of commercial L-galactose to the corresponding L-galactosaminuronic acid. Notably, the C6 oxidation of the allyl glycoside was more efficient than that of the selenoglycoside. In addition, a balance between the formation of allyl glycoside and the recovery of selenoglycoside was essential to improve efficiency of the NIS/TfOH-catalyzed allylation. This synthetically useful L-galactosaminuronic acid building block will provide a basis for the syntheses of complex bacterial glycans.