Related Experiment Video
Updated: Jul 2, 2025

High-Pressure NMR Experiments for Detecting Protein Low-Lying Conformational States
Published on: June 29, 2021
Conformational Landscape of α-Halopropiophenones Determined by JC-H NMR Reveals Unexpected Patterns and Geometric
Camila Botin Francisco1,2, Cleverton de Souza Fernandes1, Fernanda Franco Dourado1
1Department of Chemistry, State University of Maringá, 5790, Maringá 87020-900, Brazil.
Abstract:
The conformational features of α-halopropiophenones were investigated to understand the influence of α-halogens on conformation through hyperconjugative interactions, electrostatics, and steric factors. Using NMR, C-H scalar coupling constants were measured in different solvents, revealing a pattern in the conformational equilibria, which we validated by computational means. This behavior arises largely from hyperconjugative effects with the exception of the fluoro-derivatives, which are also influenced by steric and electrostatic interactions. In all cases, the contribution to hyperconjugation of the α-halo ketones is driven by the oxygen lone pair (rather than the C-X bond), which donates electron density to the adjacent C-C bonds. Additionally, C-Cα bond rotation generates distortions in the side chain, responsible for destabilization, thus affecting system conjugation. These structural features identified for the α-halo ketones are also reflected in their reactivity, which is distinct from that expected for nucleophilic addition.
More Related Videos
10:52Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
14:44Structure and Coordination Determination of Peptide-metal Complexes Using 1D and 2D 1H NMR
Published on: December 16, 2013
Related Concept Videos
¹H NMR of Conformationally Flexible Molecules: Temporal Resolution
¹H NMR of Conformationally Flexible Molecules: Variable-Temperature NMR
Conformations of Cyclohexane
The chair form is the most stable and derives its name from its resemblance to the “easy chair.” In the chair conformation, two carbon atoms are arranged out-of-plane — one above and one below, minimizing the torsional strain. In the chair form, the bond angle is very close to the ideal...
Conformations of Cycloalkanes
¹H NMR Chemical Shift Equivalence: Enantiotopic and Diastereotopic Protons
In chiral compounds such as 2-butanol, replacing the methylene hydrogens at C3 produces a pair of...
Aromatic Hydrocarbon Anions: Structural Overview
Due to the absence of continuous...