title: Alpha- and beta-glycosyl sulfonium ions: generation and reactivity.
abstract: Low-temperature electrochemical oxidation of thioglycosides gave glycosyl triflates from which glycosyl sulfonium ions were produced (see scheme). The latter were characterized by NMR spectroscopy and cold-spray mass spectrometry as a mixture of alpha- and beta-isomers (45:55). The alpha-glycosyl sulfonium ion exhibited higher reactivity than the beta-glycosyl sulfonium ion in the reaction with methanol, which gave a mixture of alpha- and beta-methyl glycosides (41:59).
authors.affiliation: Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan.
authors.forename: Toshiki
authors.initials: T
authors.lastname: Nokami
authors.forename: Akito
authors.initials: A
authors.lastname: Shibuya
authors.forename: Shino
authors.initials: S
authors.lastname: Manabe
authors.forename: Yukishige
authors.initials: Y
authors.lastname: Ito
authors.forename: Jun-ichi
authors.initials: J
authors.lastname: Yoshida
mesh_terms: D003080:Cold Temperature; D004563:Electrochemistry; D005947:Glucose / Q000031:analogs & derivatives / Q000737:chemistry; D006031:Glycosylation; D009682:Magnetic Resonance Spectroscopy; D008698:Mesylates / Q000138:chemical synthesis / Q000737:chemistry; D010084:Oxidation-Reduction; D013452:Sulfonium Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D013865:Thioglycosides / Q000737:chemistry*
chemical_list: D008698:Mesylates; D013452:Sulfonium Compounds; D013865:Thioglycosides; D005947:Glucose