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

Author(s)

Chiari, Cassia ; Batista, Patrick R. ; Viesser, Renan V. ; Schenberg, Leonardo A. ; Ducati, Lucas C. ; Linclau, Bruno ; Tormena, Claudio F.

• Document type: Journal article
• Source: ORGANIC & BIOMOLECULAR CHEMISTRY; v. 22, n. 13, p. 16-pg., 2024-02-26.

Abstract

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. (AU)

• FAPESP's process: 21/05095-6 - Conformational preferences on fluorine-containing molecules
• Grantee: Cassia Chiari
• Support Opportunities: Scholarships in Brazil - Doctorate (Direct)
• FAPESP's process: 17/20890-1 - Evaluation of shielding and transmission mechanisms of 1H, 13C and 19F NMR
• Grantee: Renan Vidal Viesser
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 19/18727-0 - Study of 199Hg organometallic compounds in solution by ab initio molecular dynamics and relativistic NMR calculations
• Grantee: Leonardo Araujo Schenberg
• Support Opportunities: Scholarships in Brazil - Doctorate (Direct)
• FAPESP's process: 17/17750-3 - Solvent Effect in NMR Parameters by ab initio Molecular Dynamics
• Grantee: Lucas Colucci Ducati
• Support Opportunities: Regular Research Grants
• FAPESP's process: 19/18193-6 - Intramolecular hydrogen bonding involving fluorine atom
• Grantee: Cassia Chiari
• Support Opportunities: Scholarships abroad - Research Internship - Scientific Initiation
• FAPESP's process: 23/00531-8 - Assessment of the solvent effect on the organic reaction mechanisms through ab initio molecular dynamics simulations
• Grantee: Patrick Rodrigues Batista
• Support Opportunities: Scholarships abroad - Research Internship - Post-doctor
• FAPESP's process: 21/09687-5 - Assessment of conformational preferences on fluorine-containing molecules and study of transmission pathway for JFH couplings using Car-Parrinello molecular dynamics
• Grantee: Patrick Rodrigues Batista
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 20/10246-0 - Nuclear magnetic resonance spectroscopy: from pulse sequences to structural assignments
• Grantee: Claudio Francisco Tormena
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 18/02634-0 - Intramolecular hydrogen bonding and conformational preferences on fluorinated amino-alcohols
• Grantee: Cassia Chiari
• Support Opportunities: Scholarships in Brazil - Scientific Initiation
• FAPESP's process: 15/08541-6 - Nuclear magnetic resonance spectroscopy: beyond molecular structure assignment
• Grantee: Claudio Francisco Tormena
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 22/10688-9 - Study of chloroform solvent effect on 199Hg NMR properties of methylmercury derivatives by ab initio molecular dynamics and relativistic calculations
• Grantee: Leonardo Araujo Schenberg
• Support Opportunities: Scholarships abroad - Research Internship - Doctorate (Direct)