| dc.creator | Silla, Josué M. | |
| dc.creator | Freitas, Matheus P. | |
| dc.date | 2020-05-12T18:27:40Z | |
| dc.date | 2020-05-12T18:27:40Z | |
| dc.date | 2019-01 | |
| dc.date.accessioned | 2023-09-28T20:00:04Z | |
| dc.date.available | 2023-09-28T20:00:04Z | |
| dc.identifier | SILLA, J. M.; FREITAS, M. P. Tautomerism and conformational analysis in 3-fluoropiperidin-2-one inform on F···HO intramolecular hydrogen bond. Journal of Fluorine Chemistry, Amsterdam, v. 217, p. 8-12, Jan. 2019. | |
| dc.identifier | https://www.sciencedirect.com/science/article/abs/pii/S002211391830383X#! | |
| dc.identifier | http://repositorio.ufla.br/jspui/handle/1/40848 | |
| dc.identifier.uri | https://repositorioslatinoamericanos.uchile.cl/handle/2250/9042039 | |
| dc.description | Whether hydroxyl hydrogen is directed towards a Lewis base substituent in an alkyl chain due to intramolecular hydrogen bonds or to avoid repulsion between the hydroxyl oxygen and the substituent is a debatable topic and difficult to probe. This is still more challenging when fluorine is the Lewis base substituent. This work reports a theoretical approach capable of dissecting the contributions from hydrogen bond and repulsion, allowing to decide which interaction dominates the orientation of the hydroxyl group in a high-energy tautomer of 3-fluoropiperidin-2-one. A comparison between the potential energy curves for the hydroxyl rotation in the axial and equatorial conformers revealed that repulsion between fluorine and oxygen contributes by ca. 1.2 kcal mol−1 to destabilize the cis isomer, while intramolecular hydrogen bond between fluorine and the hydroxyl group amounts by ca. 0.9 kcal mol−1 favoring the trans isomer. These are not the major effects governing the conformational equilibrium of the studied compound, which is rather dictated by N⋯O steric repulsion, but the obtained outcomes can be valuable to understand the role of F⋯H(O) hydrogen bonds in conformational analysis and, ultimately, in the design of performance fluorinated aliphatic alcohols. | |
| dc.language | en_US | |
| dc.publisher | Elsevier | |
| dc.rights | restrictAccess | |
| dc.source | Journal of Fluorine Chemistry | |
| dc.subject | Organofluorines | |
| dc.subject | Conformational analysis | |
| dc.subject | Hydrogen bond | |
| dc.subject | Steric repulsions | |
| dc.subject | Theoretical calculations | |
| dc.subject | Organofluorinos | |
| dc.subject | Análise conformacional | |
| dc.subject | Ligações de hidrogênio | |
| dc.subject | Repulsões estéricas | |
| dc.title | Tautomerism and conformational analysis in 3-fluoropiperidin-2-one inform on F···HO intramolecular hydrogen bond | |
| dc.type | Artigo | |
