The potency of 2-deoxy-2-fluoroglycosides in activity-based profiling of human acid β-glucosidase is drastically improved by introducing an N-phenyl trifluoroacetimidate leaving group at the anomeric center. Protonation by the general acid-base catalyst in the active site turned out to be a prerequisite, making the imidate probe a genuine mechanism-based glycosidase inactivator.

M uham m ad Saeed3, M uham m ad A bbas3, Khalid M oham m ad K hanb, and Wolfgang V oelter3 a Abteilung für Physikalische Biochemie, Physiologisch-chemisches Institut der Universität Tübingen, Hoppe-Seyler-Straße-4, D-72076 Tübingen, Germany b International Center for Chemical Sciences, H. E. J. Research Institute of Chemistry, University of Karachi, Karachi-75276, Pakistan Reprint request to Pr...

Glycoside bond formation generally requires activation of the sugar at the anomeric center. To this end, anomeric oxygen exchange reactions, resulting in the Koenigs±Knorr method and variations or, alternatively, activation through retention of the anomeric oxygen, resulting in the trichloroacetimidate method and in the phosphite method, have been proposed. The successful application of the tri...

Uronic acids are carbohydrates present in relevant biologically active compounds. Most of the latter are glycosides or oligosaccharides linked by their anomeric carbon, so their synthesis requires glycoside-bond formation. The activation of this anomeric center remains difficult due to the presence of the electron-withdrawing C-5 carboxylic group. Herein we present an overview of glucuronidatio...

Heparin and low molecular weight heparins are polydisperse polysaccharides with a degree of polymerization ranging from 4 to approximately 40. The determination of their average molecular weights has traditionally relied on size exclusion chromatography involving the use of oligosaccharides of known size and molecular weight as standards. 13C NMR spectroscopy is applied for the first time to ob...

A series of light-activatable perfluorophenylazide (PFPA)-conjugated carbohydrate structures have been synthesized and applied to glycoarray fabrication. The glycoconjugates were structurally varied with respect to anomeric attachment, S-, and O-linked carbohydrates, respectively, as well as linker structure and length. Efficient stereoselective synthetic routes were developed, leading to the f...

Correction for ‘Stereoelectronic power of oxygen in control chemical reactivity: the anomeric effect is not alone’ by Igor V. Alabugin et al. , Chem. Soc. Rev. 2021, DOI: 10.1039/d1cs00386k.