The mutual effect of a carbonyl polar bond and an endocyclic oxygen on the ¹JC-F coupling constant of fluorinated six-membered rings.

The ¹JC-F coupling constant can be useful to probe the conformational landscape of organofluorine compounds and the intramolecular interactions governing the stereochemistry of these compounds. Neighboring oxygen electron lone pairs and a carbonyl group relative to a C-F bond affect this coupling constant in an opposite way, and therefore, analysis of the interactions involving these entities simultaneously indicates which effect dominates ¹JC-F. Spin- spin coupling constant calculations for a series of fluorinated tetrahydropyrans, cyclohexanones, and dihydropyran-3-ones indicated that an electrostatic/dipolar interaction between the C-F and C-O bonds is more important than the steric interaction between the C-F bond and the oxygen electron lone pairs. An intuitive consequence of such outcome is that this interaction not only drives the coupling constant but can also be taken into account when aiming at the stereochemical control of functionalized organofluorine compounds. [ABSTRACT FROM AUTHOR]