Please use this identifier to cite or link to this item:
metadata.artigo.dc.title: Endocyclic oxygen in 3-fluorodihydro-2H-pyran-4(3H)-one that does not induce the gauche effect
metadata.artigo.dc.creator: Silva, Thayná F. B.
Andrade, Laize A. F.
Silla, Josué M.
Duarte, Claudimar J.
Rittner, Roberto
Freitas, Matheus P.
metadata.artigo.dc.subject: Fluorine
Molecular structure
metadata.artigo.dc.publisher: American Chemical Society (ACS) 25-Jul-2014
metadata.artigo.dc.identifier.citation: SILVA, T. F. B. et al. Endocyclic oxygen in 3-fluorodihydro-2H-pyran-4(3H)-one that does not induce the gauche effect. The Journal of Physical Chemistry A, [S.l.], v. 118, n. 32, p. 6266-6271, July 2014. DOI: 10.1021/jp505573x.
metadata.artigo.dc.description.abstract: 2-Fluorocyclohexanone undergoes chair inversion, giving rise to axial and equatorial conformers, with the equatorial form being highly preferred in solution, for example, 87% in chloroform and 93% in methylene chloride. Modifications in the conformational preferences can modify macroscopic properties of 2-fluoro ketones. The introduction of an endocyclic oxygen in 2-fluorocyclohexanone to give 3-fluorodihydro-2H-pyran-4(3H)-one would be expected to create a gauche effect in the axial conformer along with the O–C–C–F moiety, inducing an increase of its population. However, small changes were verified in the conformational populations both in the gas phase and solution because the carbonyl group plays an important role for the hyperconjugation in the equatorial conformer, despite experiencing strong dipolar repulsion with the fluorine atom. These data were obtained theoretically and by NMR spectroscopy, while the nature of the interactions governing these conformational shifts were investigated on the basis of natural bond orbital analysis.
metadata.artigo.dc.language: en_US
Appears in Collections:DQI - Artigos publicados em periódicos

Files in This Item:
There are no files associated with this item.

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.