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Transition-State Structure for the Quintessential SN2 Reaction of a Carbohydrate: Reaction of α‑Glucopyranosyl Fluoride with Azide Ion in Water
journal contribution
posted on 2014-09-03, 00:00 authored by Jefferson Chan, Natalia Sannikova, Ariel Tang, Andrew J. BennetWe
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 13C-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).