Transition-state structure for the quintessential SN2 reaction of a carbohydrate: Reaction of α-glucopyranosyl fluoride with azide ion in Water

Jefferson Chan; Natalia Sannikova; Ariel Tang; Andrew J. Bennet

doi:10.1021/ja506092h

Transition-state structure for the quintessential S_N2 reaction of a carbohydrate: Reaction of α-glucopyranosyl fluoride with azide ion in Water

Jefferson Chan
, Natalia Sannikova
, Ariel Tang
, Andrew J. Bennet

Research output: Contribution to journal › Article › peer-review

Abstract

We report that the S_N2 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).

Original language	English (US)
Pages (from-to)	12225-12228
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	136
Issue number	35
DOIs	https://doi.org/10.1021/ja506092h
State	Published - Sep 3 2014

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja506092h

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Cite this

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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 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).",

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AU - Bennet, Andrew J.

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AB - 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 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).

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