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Structural, mechanistic, and computational analysis of the effects of anomeric fluorines on anomeric fluoride departure in 5-fluoroxylosyl fluorides

Structural, mechanistic, and computational analysis of the effects of anomeric fluorines on anomeric fluoride departure in 5-fluoroxylosyl fluorides
Structural, mechanistic, and computational analysis of the effects of anomeric fluorines on anomeric fluoride departure in 5-fluoroxylosyl fluorides
The effects of fluorine substitution at the C-5 center of pyranosyl fluorides on the reactivity at the C-1 anomeric center was probed by studying a series of 5-fluoroxylosyl fluoride derivatives. X-ray structures of their per-O-acetates detailed the effects on the ground-state structures. First-order rate constants for spontaneous hydrolysis, in conjunction with computational studies, revealed that changes in the stereochemistry of the 5-fluorine had minimal effects on the solvolysis rate constants and that the observed rate reductions were broadly similar to those caused by additional fluorine substitution at C-1 but significantly less than those due to substitution at C-2. Differences in the trapping behavior of 5- versus 2-fluoro-substituted glycosyl fluorides with ?- and ?-glycosidases arise more from differences in steric effects and hydrogen-bonding interactions than from intrinsic reactivity differences.
0002-7863
15826-15829
Lee, Seung Seo
ee34fa26-5fb6-48c8-80c2-1f13ec4ccceb
Greig, Ian R.
69753ec8-cfc2-4bf1-99ea-103483b28c32
Vocadlo, David J.
665c7d3d-08e8-459d-a93d-e466dbc97f4e
McCarter, John D.
a1ad6ac7-ce08-4e9f-8b16-3efad4956532
Patrick, Brian O.
44faf6ae-8ba6-4cb0-bcb7-0e7261948804
Withers, Stephen G.
2fa507a8-6772-41a0-97a0-a33f443bbcc1
Lee, Seung Seo
ee34fa26-5fb6-48c8-80c2-1f13ec4ccceb
Greig, Ian R.
69753ec8-cfc2-4bf1-99ea-103483b28c32
Vocadlo, David J.
665c7d3d-08e8-459d-a93d-e466dbc97f4e
McCarter, John D.
a1ad6ac7-ce08-4e9f-8b16-3efad4956532
Patrick, Brian O.
44faf6ae-8ba6-4cb0-bcb7-0e7261948804
Withers, Stephen G.
2fa507a8-6772-41a0-97a0-a33f443bbcc1

Lee, Seung Seo, Greig, Ian R., Vocadlo, David J., McCarter, John D., Patrick, Brian O. and Withers, Stephen G. (2011) Structural, mechanistic, and computational analysis of the effects of anomeric fluorines on anomeric fluoride departure in 5-fluoroxylosyl fluorides. Journal of the American Chemical Society, 133 (40), 15826-15829. (doi:10.1021/ja204829r).

Record type: Article

Abstract

The effects of fluorine substitution at the C-5 center of pyranosyl fluorides on the reactivity at the C-1 anomeric center was probed by studying a series of 5-fluoroxylosyl fluoride derivatives. X-ray structures of their per-O-acetates detailed the effects on the ground-state structures. First-order rate constants for spontaneous hydrolysis, in conjunction with computational studies, revealed that changes in the stereochemistry of the 5-fluorine had minimal effects on the solvolysis rate constants and that the observed rate reductions were broadly similar to those caused by additional fluorine substitution at C-1 but significantly less than those due to substitution at C-2. Differences in the trapping behavior of 5- versus 2-fluoro-substituted glycosyl fluorides with ?- and ?-glycosidases arise more from differences in steric effects and hydrogen-bonding interactions than from intrinsic reactivity differences.

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Published date: 12 September 2011
Organisations: Chemistry

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Local EPrints ID: 340233
URI: http://eprints.soton.ac.uk/id/eprint/340233
ISSN: 0002-7863
PURE UUID: ac8b3d9f-9deb-4c79-819c-e64af773ac5c
ORCID for Seung Seo Lee: ORCID iD orcid.org/0000-0002-8598-3303

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Date deposited: 15 Jun 2012 14:32
Last modified: 12 Nov 2019 01:37

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Contributors

Author: Seung Seo Lee ORCID iD
Author: Ian R. Greig
Author: David J. Vocadlo
Author: John D. McCarter
Author: Brian O. Patrick
Author: Stephen G. Withers

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