Determining the Factors Accounting for Reaction Selectivity: A Relative Energy Gradient – Interacting Quantum Atoms and Natural Bonding Orbitals Study DOI Creative Commons
Aël Cador, Christophe Morell, Vincent Tognetti

и другие.

ChemPhysChem, Год журнала: 2024, Номер 25(16)

Опубликована: Май 15, 2024

Identifying the main physicochemical properties accounting for course of a reaction is utmost importance to rationalize chemical syntheses. To this aim, relative energy gradient (REG) method an appealing approach because it unbiased and automatic process extract most relevant pieces information. Initially formulated within interacting quantum atoms (IQA) framework single reaction, here we extend REG natural bond orbitals (NBO) analysis case two competitive processes. This development enables determination driving forces any selectivity. We illustrate extended on study ring opening in cyclobutenes, which important instance so-called torquoselectivity.

Язык: Английский

Cascade synthetic strategies opening access to medicinal-relevant aliphatic 3- and 4-membered N-heterocyclic scaffolds DOI
Daniel Łowicki, Piotr Przybylski

European Journal of Medicinal Chemistry, Год журнала: 2022, Номер 238, С. 114438 - 114438

Опубликована: Май 6, 2022

Язык: Английский

Процитировано

20
Probing Non-Covalent Interactions through Molecular Balances: A REG-IQA Study DOI Creative Commons
Fabio Falcioni,

Sophie Bennett,

Pallas Stroer-Jarvis

и другие.

Molecules, Год журнала: 2024, Номер 29(5), С. 1043 - 1043

Опубликована: Фев. 28, 2024

The interaction energies of two series molecular balances (1-X with X = H, Me, OMe, NMe2 and 2-Y Y CN, NO2, NMe2) designed to probe carbonyl…carbonyl interactions were analysed at the B3LYP/6-311++G(d,p)-D3 level theory using energy partitioning method Interacting Quantum Atoms/Fragments (IQA/IQF). partitioned are by Relative Energy Gradient (REG) method, which calculates correlation between these total a system, thereby explaining role atoms have in energetic behaviour system. traditional “back-of-the-envelope” open closed conformations do not correspond those lowest energy. Hence, more care needs be taken when considering geometries use for comparison experiment. REG-IQA shows that 1-H 1-OMe behave differently 1-Me 1-NMe2 because latter show prominent electrostatics carbonyl groups undergoes larger dihedral rotation due bulkiness functional groups. For balance, same across as balances. From an atomistic point view, formation conformer is favoured polarisation charge-transfer effects on amide bond all counterbalanced de-pyramidalisation nitrogen. Moreover, focusing oxygen α-carbon remaining group, major conformer, goes against well-known n-π* orbital overlap concept. However, REG-IQF exchange–correlation overtake working fragments around groups, while they act par 1-NMe2. also balance correlated inductive electron-donating -withdrawing trends aromatic We demonstrate methods such REG-IQA/IQF can help fine-tuning prior experiment govern probed highly dependent involved.

Язык: Английский

Процитировано

3
Hydroboration of imines: intermolecularvs.intramolecular hydride transfer DOI
Siyuan Zhai, D. Vidović, Milena Petković

и другие.

New Journal of Chemistry, Год журнала: 2023, Номер 47(24), С. 11544 - 11556

Опубликована: Янв. 1, 2023

We performed a detailed experimental and theoretical analysis of the 1,3-hydride shift in imine–BH 3 adducts, which represents crucial step formation mono-aminoboranes (R 2 N–BH ).

Язык: Английский

Процитировано

3
How to Compute Atomistic Insight in DFT Clusters: The REG-IQA Approach DOI Creative Commons
Fabio Falcioni, Paul L. A. Popelier

Journal of Chemical Information and Modeling, Год журнала: 2023, Номер 63(14), С. 4312 - 4327

Опубликована: Июль 10, 2023

The relative energy gradient (REG) method is paired with the topological partitioning interacting quantum atoms (IQA), as REG-IQA, to provide detailed and unbiased knowledge on intra- interatomic interactions. REG operates a sequence of geometries representing dynamical change system. Its recent application peptide hydrolysis human immunodeficiency virus-1 (HIV-1) protease (PDB code: 4HVP) has demonstrated its full potential in recovering reaction mechanisms through-space electrostatic exchange–correlation effects, making it compelling tool for analyzing enzymatic reactions. In this study, computational efficiency REG-IQA 133-atom HIV-1 mechanical system analyzed every detail substantially improved by means three different approaches. first approach smaller integration grids IQA integrations reduces overhead about factor 3. second uses line-simplification Ramer–Douglas–Peucker (RDP) algorithm, which outputs minimal number necessary analysis predetermined root mean squared error (RMSE) tolerance. This cuts time whole 2 if an RMSE 0.5 kJ/mol considered. third consists “biased” or “unbiased” selection specific subset initial model wave-function, results more than 10-fold speed-up per geometry calculation, without deterioration outcome analysis. Finally, show capability these approaches, findings gathered from are also applied named haloalcohol dehalogenase (HheC). summary, study takes computationally feasible highly accurate level, viable multitude systems.

Язык: Английский

Процитировано

2
Determining the Factors Accounting for Reaction Selectivity: A Relative Energy Gradient – Interacting Quantum Atoms and Natural Bonding Orbitals Study DOI Creative Commons
Aël Cador, Christophe Morell, Vincent Tognetti

и другие.

ChemPhysChem, Год журнала: 2024, Номер 25(16)

Опубликована: Май 15, 2024

Identifying the main physicochemical properties accounting for course of a reaction is utmost importance to rationalize chemical syntheses. To this aim, relative energy gradient (REG) method an appealing approach because it unbiased and automatic process extract most relevant pieces information. Initially formulated within interacting quantum atoms (IQA) framework single reaction, here we extend REG natural bond orbitals (NBO) analysis case two competitive processes. This development enables determination driving forces any selectivity. We illustrate extended on study ring opening in cyclobutenes, which important instance so-called torquoselectivity.

Язык: Английский

Процитировано

0