Mimicking Real Catalysts: Model Stepped Nickel Surfaces in Furfural Catalysis─Insights into Adsorption, Reactivity, and Defect-Driven Conversion Pathways DOI Creative Commons
Sotirios Tsatsos, Georgios Kyriakou

The Journal of Physical Chemistry Letters, Journal Year: 2025, Volume and Issue: unknown, P. 3022 - 3033

Published: March 17, 2025

The catalytic conversion of furanic compounds into renewable chemicals is essential for sustainable manufacturing. Here, we report a unique self-hydrogenation pathway furfural to 2-methylfuran on Ni(119) surface, showing how steps and nickel carbides govern reaction selectivity. Thermal desorption spectroscopic measurements reveal that undergoes decarbonylation furan terraces, while step sites act as "hydrogen transfer pumps", abstracting hydrogen from facilitating its diffusion terrace-bound molecules, thereby promoting selective hydrogenation 2-methylfuran. Moreover, the surface-bound enhances hydrogenolysis, with product selectivity closely connected concentration. DFT calculations show preference top edges, where strong bonding electron redistribution stabilize intermediates promote transformations. We further demonstrate these insights provide framework designing advanced catalysts through surface structure optimization. By linking model real-world applications, this approach enables development efficient tailored biomass conversion.

Language: Английский

First report on pesticide sub-chronic and chronic toxicities against dogs using QSAR and chemical read-across DOI
Ankur Kumar, Probir Kumar Ojha, Kunal Roy

et al.

SAR and QSAR in environmental research, Journal Year: 2024, Volume and Issue: 35(3), P. 241 - 263

Published: Feb. 23, 2024

Excessive use of chemicals is the outcome industrialization agricultural sectors which leads to disturbance ecological balance. Various agrochemicals are widely used in fields, urban green areas, and protect from various pest-associated diseases. Due their long-term health environmental hazards, chronic toxicity assessment crucial. Since vivo vitro assessments costly, lengthy, require a large number animal experiments, silico approaches better alternatives save time, cost, experimentation. We have developed first regression-based 2D-QSAR models using different sub-chronic data pesticides against dogs employing 2D descriptors. From statistical results (

Language: Английский

Citations

7
Lewis Acid‐Catalyzed Diels‐Alder Reactions: Reactivity Trends across the Periodic Table DOI Creative Commons
Pascal Vermeeren, Marco Dalla Tiezza, Michelle van Dongen

et al.

Chemistry - A European Journal, Journal Year: 2021, Volume and Issue: 27(41), P. 10610 - 10620

Published: March 29, 2021

The catalytic effect of various weakly interacting Lewis acids (LAs) across the periodic table, based on hydrogen (Group 1), pnictogen 15), chalcogen 16), and halogen 17) bonds, Diels-Alder cycloaddition reaction between 1,3-butadiene methyl acrylate was studied quantum chemically by using relativistic density functional theory. Weakly LAs accelerate lowering barrier up to 3 kcal mol

Language: Английский

Citations

33
Origin of asynchronicity in Diels–Alder reactions DOI Creative Commons
Pascal Vermeeren, Trevor A. Hamlin, F. Matthias Bickelhaupt

et al.

Physical Chemistry Chemical Physics, Journal Year: 2021, Volume and Issue: 23(36), P. 20095 - 20106

Published: Jan. 1, 2021

Quantum chemical activation strain analyses reveal that asynchronicity in Diels–Alder reactions reduces both destabilizing Pauli repulsion as well stabilizing orbital interactions, and occurs if the former dominates.

Language: Английский

Citations

33
Enantioselective Povarov Reactions: An Update of a Powerful Catalytic Synthetic Methodology DOI

Bárbara C. Lemos,

Éclair Venturini Filho, Rodolfo G. Fiorot

et al.

European Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 2022(2)

Published: Dec. 21, 2021

Abstract The enantioselective Povarov reaction is one of the most powerful synthetic strategy to synthesize chiral, highly functionalized 1,2,3,4‐tetrahydroquinolines. present Minireview aims collect significant successful examples efficient catalytic protocols for this reaction, since 2014. A comprehensive discussion different strategies employed in recent years realize provided; use chiral phosphoric acids, thio(urea) and proline derivatives, as well transition metal complexes will be presented. Additionally, critically discusses intriguing yet obscure mechanistic pathways well‐known controversial dispute between a concerted or polar two‐step process.

Language: Английский

Citations

32
Origins of Lewis acid acceleration in nickel-catalysed C–H, C–C and C–O bond cleavage DOI
Han Gao,

Lingfei Hu,

Yanlei Hu

et al.

Catalysis Science & Technology, Journal Year: 2021, Volume and Issue: 11(13), P. 4417 - 4428

Published: Jan. 1, 2021

The effects of charge transfer, Pauli repulsion and electrostatics/polarization are identified as dominant factors for Lewis acid accelerations in Ni-catalyzed C–X (X = H, C O) bond cleavages.

Language: Английский

Citations

31
Origin of the Bürgi‐Dunitz Angle DOI Creative Commons
Humberto A. Rodríguez, F. Matthias Bickelhaupt, Israel Fernández

et al.

ChemPhysChem, Journal Year: 2023, Volume and Issue: 24(17)

Published: June 12, 2023

The Bürgi-Dunitz (BD) angle plays a pivotal role in organic chemistry to rationalize the nucleophilic addition carbonyl groups. Yet, origin of obtuse trajectory nucleophile remains incompletely understood. Herein, we quantify importance underlying physical factors quantum chemically. BD appears originate from concerted action reduced Pauli repulsion between HOMO and π bond, more stabilizing HOMO-π*-LUMO(C=O) interaction, as well favorable electrostatic attraction.

Language: Английский

Citations

12
Lewis Acid-Catalyzed Carbonyl-Ene Reaction: Interplay between Aromaticity, Synchronicity, and Pauli Repulsion DOI Creative Commons
Humberto A. Rodríguez, Daniel A. Cruz, Juan I. Padrón

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(15), P. 11102 - 11110

Published: July 24, 2023

The physical factors governing the catalysis in Lewis acid-promoted carbonyl-ene reactions have been explored detail quantum chemically. It is found that binding of a acid to carbonyl group directly involved transformation greatly accelerates reaction by decreasing corresponding activation barrier up 25 kcal/mol. makes process much more asynchronous and transition state less in-plane aromatic. remarkable acceleration induced catalyst ascribed, means strain model energy decomposition analysis methods, mainly significant reduction Pauli repulsion between key occupied π-molecular orbitals reactants not widely accepted stabilization LUMO enophile.

Language: Английский

Citations

12
Origins of Regioselectivity in CuH-Catalyzed Hydrofunctionalization of Alkenes DOI

Lingfei Hu,

Han Gao, Yanlei Hu

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(5), P. 2750 - 2757

Published: Feb. 15, 2023

Factors controlling the regioselectivity in alkene hydrocupration were computationally investigated using energy decomposition analysis. The results demonstrate that Markovnikov-selective with electronically activated mono-substituted olefins is mostly affected by destabilizing Pauli repulsion, which due to electron delocalization effect. anti-Markovnikov-selective 1,1-dialkyl-substituted terminal dominated repulsive electrostatic interactions, because of unequal π distribution caused induction effect alkyl substituents.

Language: Английский

Citations

11
Unraveling the Bürgi-Dunitz Angle with Precision: The Power of a Two-Dimensional Energy Decomposition Analysis DOI Creative Commons
Israel Fernández, F. Matthias Bickelhaupt, Dennis Svatunek

et al.

Journal of Chemical Theory and Computation, Journal Year: 2023, Volume and Issue: 19(20), P. 7300 - 7306

Published: Oct. 4, 2023

Understanding the geometrical preferences in chemical reactions is crucial for advancing field of organic chemistry and improving synthetic strategies. One such preference, Bürgi-Dunitz angle, central to nucleophilic addition involving carbonyl groups. This study successfully employs a novel two-dimensional Distortion-Interaction/Activation-Strain Model combination with Energy Decomposition Analysis investigate origins angle reaction CN- (CH3)2C═O. We constructed 2D potential energy surface defined by distance between nucleophile carbonylic carbon atom attack followed an in-depth exploration components, including strain interaction energy. Our analysis reveals that emerges from delicate balance two key factors: High energy, as result compound distorting avoid Pauli repulsion, encountered at high angles, thus setting upper bound. On other hand, shaped dominant repulsion when angles are lower. work emphasizes value refined tool, offering both quantitative qualitative insights into reactivity selectivity.

Language: Английский

Citations

11
Click Organocatalysis: Acceleration of Azide–Alkyne Cycloadditions with Mutually Orthogonal Click Reactions DOI
Brian J. Levandowski, Brian J. Graham, K. N. Houk

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(4), P. 2232 - 2237

Published: Jan. 26, 2024

"Click organocatalysis" uses mutually orthogonal click reactions to organocatalyze a reaction. We report the development of an isobenzofuran organocatalyst that increases rate and regioselectivity azide-alkyne cycloaddition. The organocatalytic cycle consists (1) Diels-Alder reaction alkyne with diarylisobenzofuran form benzooxanorbornadiene, (2) 1,3-dipolar cycloaddition azide 4,5-dihydro-1,2,3-triazole, (3) retro-Diels-Alder releases triazole product regenerates organocatalyst. was computationally designed catalyze perfluorophenyl methyl propiolate selectively 1,4-triazole product. Experimental validation obtained 4-azido-2,3,5,6-tetrafluorobenzoate propiolate.

Language: Английский

Citations

4