title: Transition-state structure for the quintessential SN2 reaction of a carbohydrate: reaction of α-glucopyranosyl fluoride with azide ion in water.
abstract: We report that the SN2 reaction of α-d-glucopyranosyl fluoride with azide ion proceeds through a loose (exploded) transition-state (TS) structure. We reached this conclusion by modeling the TS using a suite of five experimental kinetic isotope effects (KIEs) as constraints for the calculations. We also report that the anomeric (13)C-KIE is not abnormally large (k12/k13 = 1.024 ± 0.006), a finding which is at variance with the previous literature value (Zhang et al. J. Am. Chem. Soc. 1994, 116, 7557).
authors.affiliation: Chemistry Department, Simon Fraser University , 8888 University Drive, Burnaby, British Columbia V5A 1S6, Canada.
authors.forename: Jefferson
authors.initials: J
authors.lastname: Chan
authors.forename: Natalia
authors.initials: N
authors.lastname: Sannikova
authors.forename: Ariel
authors.initials: A
authors.lastname: Tang
authors.forename: Andrew J
authors.initials: AJ
authors.lastname: Bennet
mesh_terms: D001386:Azides / Q000737:chemistry*; D005947:Glucose / Q000031:analogs & derivatives* / Q000737:chemistry; D007477:Ions / Q000737:chemistry; D007700:Kinetics; D008958:Models, Molecular; D014867:Water / Q000737:chemistry*
chemical_list: D001386:Azides; D007477:Ions; D014867:Water; C030364:glucosyl fluoride; D005947:Glucose