The concise synthesis of a potentially “super-armed” glucuronidation donor is reported. The α-anomer was crystallized and analyzed by single crystal X-ray diffraction. The pyranose ring was found to be in a twist-boat conformation in the solid state. To confirm the relevance of this finding for the solution state, and explain the failure of analysis by NMR, DFT calculations were performed. They revealed the twist-boat to be the dominant among a group of several possible conformers at ambient temperature. Graphical abstract