title: Catching elusive glycosyl cations in a condensed phase with HF/SbF₅ superacid.
abstract: Glycosyl cations are universally accepted key ionic intermediates in the mechanism of glycosylation, the reaction that covalently links carbohydrates to other molecules. These ions have remained hypothetical species so far because of their extremely short life in organic media as a consequence of their very high reactivity. Here, we report the use of liquid hydrofluoric acid-antimony pentafluoride (HF/SbF5) superacid to generate and stabilize the glycosyl cations derived from peracetylated 2-deoxy and 2-bromoglucopyranose in a condensed phase. Their persistence in this superacid medium allows their three-dimensional structure to be studied by NMR, aided by complementary computations. Their deuteration further confirms the impact of the structure of the glycosyl cation on the stereochemical outcome of its trapping.
authors.affiliation: Université de Poitiers, UMR-CNRS 7285, IC2MP, Equipe 'Synthèse organique', 4 rue Michel Brunet, TSA 51106, Poitiers Cedex 9 86073, France.
authors.forename: A
authors.initials: A
authors.lastname: Martin
authors.affiliation: CIC bioGUNE, Parque Tecnológico de Bizkaia, Edif. 801A-1°, Derio-Bizkaia 48160, and Ikerbasque, Basque Foundation for Science, Maria López de Haro 3, 48013 Bilbao, Spain.
authors.forename: A
authors.initials: A
authors.lastname: Arda
authors.affiliation: Université de Poitiers, UMR-CNRS 7285, IC2MP, Equipe 'Synthèse organique', 4 rue Michel Brunet, TSA 51106, Poitiers Cedex 9 86073, France.
authors.forename: J
authors.initials: J
authors.lastname: Désiré
authors.affiliation: Université de Poitiers, UMR-CNRS 7285, IC2MP, Equipe 'Synthèse organique', 4 rue Michel Brunet, TSA 51106, Poitiers Cedex 9 86073, France.
authors.forename: A
authors.initials: A
authors.lastname: Martin-Mingot
authors.affiliation: Université de Poitiers, UMR-CNRS 7285, IC2MP, Equipe 'Synthèse organique', 4 rue Michel Brunet, TSA 51106, Poitiers Cedex 9 86073, France.
authors.forename: N
authors.initials: N
authors.lastname: Probst
authors.affiliation: Sorbonne Universités, UPMC Univ Paris 06, UMR CNRS 8232, IPCM, LabEx MiChem, F-75005 Paris, France.
authors.forename: P
authors.initials: P
authors.lastname: Sinaÿ
authors.affiliation: CIC bioGUNE, Parque Tecnológico de Bizkaia, Edif. 801A-1°, Derio-Bizkaia 48160, and Ikerbasque, Basque Foundation for Science, Maria López de Haro 3, 48013 Bilbao, Spain.
authors.forename: J
authors.initials: J
authors.lastname: Jiménez-Barbero
authors.affiliation: Université de Poitiers, UMR-CNRS 7285, IC2MP, Equipe 'Synthèse organique', 4 rue Michel Brunet, TSA 51106, Poitiers Cedex 9 86073, France.
authors.forename: S
authors.initials: S
authors.lastname: Thibaudeau
authors.affiliation: Université de Poitiers, UMR-CNRS 7285, IC2MP, Equipe 'Synthèse organique', 4 rue Michel Brunet, TSA 51106, Poitiers Cedex 9 86073, France.
authors.forename: Y
authors.initials: Y
authors.lastname: Blériot
mesh_terms: D040761:Biomimetic Materials / Q000737:chemistry*; D002412:Cations / Q000737:chemistry*; D006031:Glycosylation; D006858:Hydrofluoric Acid / Q000737:chemistry*; D015394:Molecular Structure
chemical_list: D002412:Cations; D006858:Hydrofluoric Acid