Beilstein J Org Chem. 2017 Aug 24;13:1781-1787. doi: 10.3762/bjoc.13.172. eCollection 2017.
Conformational impact of structural modifications in 2-fluorocyclohexanone.
Beilstein journal of organic chemistry
Francisco A Martins, Josué M Silla, Matheus P Freitas
Affiliations
Affiliations
- Department of Chemistry, Federal University of Lavras, 37200-000, Lavras, MG, Brazil.
PMID: 28904621
PMCID: PMC5588668 DOI: 10.3762/bjoc.13.172
Abstract
2-Haloketones are building blocks that combine physical, chemical and biological features of materials and bioactive compounds, while organic fluorine plays a fundamental role in the design of performance organic molecules. Since these features are dependent on the three-dimensional chemical structure of a molecule, simple structural modifications can affect its conformational stability and, consequently, the corresponding physicochemical/biological property of interest. In this work, structural changes in 2-fluorocyclohexanone were theoretically studied with the aim at finding intramolecular interactions that induce the conformational equilibrium towards the axial or equatorial conformer. The interactions evaluated were hydrogen bonding, hyperconjugation, electrostatic and steric effects. While the gauche effect, originated from hyperconjugative interactions, does not appear to cause some preferences for the axial conformation of organofluorine heterocycles, more classical effects indeed rule the conformational equilibrium of the compounds. Spectroscopic parameters (NMR chemical shifts and coupling constants), which can be useful to determine the stereochemistry and the interactions operating in the series of 2-fluorocyclohexanone derivatives, were also calculated.
Keywords: 2-fluorocyclohexanone; classical effects; conformational analysis; hyperconjugation
References
- Angew Chem Int Ed Engl. 2007;46(31):5904-8 - PubMed
- J Phys Chem A. 2014 Jan 16;118(2):503-7 - PubMed
- Org Lett. 2002 Oct 17;4(21):3557-60 - PubMed
- Chemistry. 2005 Feb 18;11(5):1579-91 - PubMed
- Beilstein J Org Chem. 2014 Apr 16;10:877-82 - PubMed
- Chem Rev. 2005 Aug;105(8):2999-3093 - PubMed
- J Org Chem. 2014 Jul 3;79(13):6385-8 - PubMed
- J Phys Chem A. 2014 Aug 14;118(32):6266-71 - PubMed
- Phys Chem Chem Phys. 2008 Nov 28;10(44):6615-20 - PubMed
- J Org Chem. 2012 Apr 20;77(8):3689-99 - PubMed
- Chem Commun (Camb). 2012 Feb 28;48(18):2433-5 - PubMed
- Magn Reson Chem. 2009 Apr;47(4):348-51 - PubMed
- J Phys Chem A. 2005 Feb 17;109(6):1223-9 - PubMed
Publication Types