Molecular dynamics and NMR reveal the coexistence of H-bond-assisted and through-space JFH coupling in fluorinated amino alcohols

The J(FH) coupling constants in fluorinated amino alcohols were investigated through experimental and theoretical approaches. The experimental J(FH) couplings were only reproduced theoretically when explicit solvation through molecular dynamics (MD) simulations was conducted in DMSO as the solvent....

Full description

Saved in:
Bibliographic Details
Published inOrganic & biomolecular chemistry Vol. 22; no. 13; pp. 2580 - 2595
Main Authors Chiari, Cassia, Batista, Patrick R., Viesser, Renan V., Schenberg, Leonardo A., Ducati, Lucas C., Linclau, Bruno, Tormena, Claudio F.
Format Journal Article
LanguageEnglish
Published CAMBRIDGE Royal Soc Chemistry 27.03.2024
Royal Society of Chemistry
Subjects
Alcohols
Chemistry
Chemistry, Organic
Coexistence
Conformation
Coupling (molecular)
Couplings
Fluorination
Fluorine
Hydrogen
Hydrogen bonding
Hydrogen bonds
Molecular dynamics
NMR
Nuclear magnetic resonance
Physical Sciences
Science & Technology
Solvation
Spin-spin coupling
PATHWAYS
CONSTANTS
DERIVATIVES NMR
SPIN
INTRAMOLECULAR HYDROGEN-BOND
CHEMICAL-SHIFTS
H-1-F-19
2ND ROW ATOMS
DIMETHYL-SULFOXIDE
GAUSSIAN-BASIS SETS
Online AccessGet full text

Cover

More Information
Summary:The J(FH) coupling constants in fluorinated amino alcohols were investigated through experimental and theoretical approaches. The experimental J(FH) couplings were only reproduced theoretically when explicit solvation through molecular dynamics (MD) simulations was conducted in DMSO as the solvent. The combination of MD conformation sampling and DFT NMR spin-spin coupling calculations for these compounds reveals the simultaneous presence of through-space (TS) and hydrogen bond (H-bond) assisted J(FH) coupling between fluorine and hydrogen of the NH group. Furthermore, MD simulations indicate that the hydrogen in the amino group participates in both an intermolecular bifurcated H-bond with DMSO and in transmitting the observed J(FH) coupling. The contribution of TS to the J(FH) coupling is due to the spatial proximity of the fluorine and the NH group, aided by a combination of the non-bonding transmission pathway and the hydrogen bonding pathway. The experimental J(FH) coupling observed for the molecules studied should be represented as (4TS/1h)J(FH) coupling.
Bibliography:ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:1477-0520
1477-0539
DOI:10.1039/d4ob00049h