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

Article Chemistry, Applied

Regioselective N-Functionalization of Tautomerizable Heterocycles through Methyl Trifluoromethanesulfonate-Catalyzed Substitution of Alcohols and Alkyl Group Migrations

Surajit Duari et al.

Summary: In this study, a catalytic synthetic strategy was developed to access various N-functionalized heterocyclic derivatives. The reaction involves the direct nucleophilic substitution of alcohols followed by X to N alkyl group migration. Methyl trifluoromethanesulfonate was found to be an efficient catalyst for this reaction. The mechanism was elucidated through experiments and DFT calculations.

ADVANCED SYNTHESIS & CATALYSIS (2022)

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Article Chemistry, Organic

Regioselection Switch in Nucleophilic Addition to Isoquinolinequinones: Mechanism and Origin of the Regioselectivity in the Total Synthesis of Ellipticine

Joaquim A. M. Castro et al.

Summary: Ellipticine was synthesized from 2,5-dimethoxyisoquinoline in six steps with a 20% global yield. The regioselective control of nucleophilic attack on isoquinoline-5,8-dione is described for the first time. Density functional theory calculations revealed the unexpected role of N-oxide in cascade tautomerizations and nucleophilic attack, accelerating the overall process.

JOURNAL OF ORGANIC CHEMISTRY (2022)

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Article Chemistry, Physical

Solvent Effects on the Menshutkin Reaction

Haydar Taylan Turan et al.

Summary: In this study, the energetics and solvent distributions for the NH3+MeCl and Pyr+MeBr reactions were investigated using reactive molecular dynamics simulations. It was found that polar solvents and benzene exhibited strong to moderate catalytic effects, while the apolar and bulky cyclohexane showed weak interactions with the solute. The solvents' distributions changed considerably between the reactant and transition state, but showed comparatively little change between the transition state and product conformations of the solute.

JOURNAL OF PHYSICAL CHEMISTRY B (2022)

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Article Chemistry, Multidisciplinary

Benchmark Density Functional Theory Approach for the Calculation of Bond Dissociation Energies of the M-O2 Bond: A Key Step in Water Splitting Reactions

Naveen Kosar et al.

Summary: This study evaluates the performance of density functional theory methods in measuring bond dissociation energies (BDEs) of M-O-2 bonds in water splitting reactions. The results suggest that the combination of B3LYP-GD3BJ functional and LANL2DZ & 6-31G(d) basis sets provides an efficient, cost-effective, precise, and accurate method.

ACS OMEGA (2022)

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Article Chemistry, Physical

Theoretical investigation of the cooperative effect of solvent: a case study

Caio M. Porto et al.

Summary: This study investigates the effect of solvent on the reaction at the DFT level and suggests a new pathway for the addition reaction of HCl to 1-butene by incorporating the solvent. It is found that implicit solvent provides greater stabilization for the reaction coordinates and transition states. The study also reveals that the number of explicit solvent molecules added significantly influences the calculated reaction rates.

PHYSICAL CHEMISTRY CHEMICAL PHYSICS (2022)

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Article Chemistry, Physical

MP2 versus density functional theory calculations in CO2-sequestration reactions with anions: Basis set extrapolation and solvent effects

Daniel G. S. Quattrociocchi et al.

Summary: This study investigated the interaction between various anions and CO2 through electronic structure calculations, revealing different thermodynamic properties of the reactions under different conditions. The solvent effect reduced the exothermicity of the reactions and induced intrinsic activation barriers.

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY (2021)

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Article Chemistry, Physical