Solvent Effects in the Regioselective N-Functionalization of Tautomerizable Heterocycles Catalyzed by Methyl Trifluoromethanesulfonate: A Density Functional Theory Study with Implicit Solvent Model

Methyl trifluoromethanesulfonate was found to catalyze the reaction of the nucleophilic substitution of the hydroxyl group of alcohols by N-heterocycles followed by X- to N- alkyl group migration (X = O, S) to obtain N-functionalized benzoxazolone, benzothiazolethione, indoline, benzoimidazolethione...

Full description

Saved in:
Bibliographic Details
Published inComputation Vol. 10; no. 10; p. 172
Main Authors Morgon, Nelson H., Biswas, Srijit, Duari, Surajit, de Souza, Aguinaldo R.
Format Journal Article
LanguageEnglish
Published Basel MDPI AG 01.09.2022
Subjects
Acetonitrile
Alcohols
Antibiotics
Basis functions
Chemical reactions
Chloroform
Density functional theory
Density functionals
Dichloroethane
Dumping
Energy
Enthalpy
Force and energy
Free energy
Hydroxyl groups
methyl trifluoromethanesulfonate
Optimization
Potential energy
potential energy surface
Solvation
Solvent effect
solvent effects
Solvents
Substitution reactions
Online AccessGet full text

Cover

More Information
Summary:Methyl trifluoromethanesulfonate was found to catalyze the reaction of the nucleophilic substitution of the hydroxyl group of alcohols by N-heterocycles followed by X- to N- alkyl group migration (X = O, S) to obtain N-functionalized benzoxazolone, benzothiazolethione, indoline, benzoimidazolethione and pyridinone derivatives. A high degree of solvent dependency on the yield of the products was observed during optimization of the reaction parameters. The yield of the product was found to be 0%, 48% and 70% in acetonitrile, 1,2-dichloroethane and chloroform, respectively. The mechanism of the reaction was established through experiments as well as DFT calculations. The functional B3LYP and 6-311++G(d) basis function sets were used to optimize the molecular geometries. D3 Grimme empiric dispersion with Becke–Johnson dumping was employed, and harmonic vibrational frequencies were calculated to characterize the stationary points on the potential energy surface. To ensure that all the stationary points were smoothly connected to each other, intrinsic reaction coordinate (IRC) analyses were performed. The influence of solvents was considered using the solvation model based on density (SMD). The free energy profiles of the mechanisms were obtained with vibrational unscaled zero-point vibrational energy (ZPE), thermal, enthalpy, entropic and solvent corrections.
ISSN:2079-3197
2079-3197
DOI:10.3390/computation10100172