title: Origin of Fluorine/Sulfur Gauche Effect of β-Fluorinated Thiol, Sulfoxide, Sulfone, and Thionium Ion.
abstract: The well-known gauche preference in FCCX systems, where X is an electronegative element from Period 2, is widely exploited in synthetic, medicinal, and material chemistry. It is rationalized on the basis of σ(C-H) → σ*(C-F) hyperconjugation and electrostatic interactions. The recent report (Thiehoff, C.; et al. Chem. Sci. 2015, 6, 3565) showed that the fluorine gauche effect can extend to Period 3 elements, such as sulfur. The aim of the present work is to disclose factors governing conformational behavior of FCCS containing systems. We examine conformational preferences in seven classes of compounds by ab initio and DFT calculations and rationalize the results by quantitatively decomposing the anti/gauche isomerization energy into contributions from electrostatic, orbital, dispersion, and Pauli interactions, and energy spent on structural changes. The results show that the fluorine/sulfur gauche effect is primarily electrostatic (63-75%), while all orbital interactions contribute 22-41% to stabilizing interactions. Stereoelectronic effects, involved in orbital interactions, also play a role in gauche conformer stabilization.
authors.affiliation: Center for Chemistry ICTM, University of Belgrade , P.O. Box 473, 11000 Belgrade, Serbia.
authors.forename: Jovana
authors.initials: J
authors.lastname: Aleksić
authors.affiliation: Center for Chemistry ICTM, University of Belgrade , P.O. Box 473, 11000 Belgrade, Serbia.
authors.forename: Milovan
authors.initials: M
authors.lastname: Stojanović
authors.affiliation: Faculty of Chemistry, University of Belgrade , Studentski trg 12-16, P.O. Box 158, 11000 Belgrade, Serbia.
authors.forename: Marija
authors.initials: M
authors.lastname: Baranac-Stojanović