Key Mechanistic Features in Palladium-Catalyzed Methylcyclopropanation of Norbornenes With Vinyl Bromides: Insights From DFT Calculations

Fang, Ying; Zhang, Yutong; Xiang, Chuyue; Song, Zhijun; Bao, Weiliang

doi:10.3389/fchem.2019.00169

Cited by 5 publications

(4 citation statements)

References 82 publications

(85 reference statements)

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“…The density functional theory (DFT) is a suitable approximation method for the theoretical study of organometallic compounds. Recent publications show that DFT gives appropriate results in studying the mechanism of palladium‐catalyzed condensation and isomerization reactions, including reactions with aryl iodides, [46,47] C−H activation, [48] tandem reaction, [49] and condensation of norbornenes [47,50] . As an object of calculations, we chose the reaction of O ‐methyloxime ( 1 ) with PhI to minimize computational costs.…”

Section: Resultsmentioning

confidence: 99%

Unusual Ring Opening of Bicyclic Terpenes During Pd‐Catalyzed Coupling with Aromatic Halides

Shutovskaya,

Ustimenko,

Tkachev

et al. 2023

Adv Synth Catal

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Herein we describe Pd‐catalyzed cross‐coupling reaction of α‐pinene derivative – pinacarvone O‐methyl oxime (1) with aryl halides (2). Surprisingly, the formation of the C−C coupling product was accompanied by an unexpected opening of the pinene bicyclic structure. The (Z)‐2‐aryl‐4,4,5‐trimethylcyclohexa‐2,5‐dien‐1‐one O‐methyl oxime (3) was formed as the resulting product. The reaction conditions of the developed synthetic procedure were carefully optimized and the reaction mechanism was supposed on the basis of data obtained by structural and computational methods.

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Section: Resultsmentioning

confidence: 99%

Unusual Ring Opening of Bicyclic Terpenes During Pd‐Catalyzed Coupling with Aromatic Halides

Shutovskaya,

Ustimenko,

Tkachev

et al. 2023

Adv Synth Catal

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“…The Gibbs free energy for each species on the potential energy profiles was taken as the sum of the thermal correction to free energies in gas phase and the single-point energy in solution. Although it has been validated by previous calculations, [47,48] the entropy corrections were not taken into consideration in this work. All calculations were performed with the Gaussian 09 software package.…”

Section: Computational Detailsmentioning

confidence: 93%

DFT Study on Dinuclear Palladium Complex Catalyzed Pyrrole Formation From tert‐Butyl Isocyanide and Alkynes

Lai

2021

ChemCatChem

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Density functional theory calculations were carried out to study the mechanisms of Pd-catalyzed reactions of alkynes with tertbutyl isocyanide forming pyrroles. In the case of di-palladium catalysis, the calculations indicated that alkyne insertion, isocyanide insertion, intramolecular cyclization, isocyanide insertion, isomerization and ligand substitution were involved in the mechanism. The intramolecular cyclization process was calculated to be the rate-determining step in the catalytic cycle. The substituent effects on the regioselectivity of reaction were also analyzed. In addition, detailed calculations on monopalladium catalysis showed that the activity of mononuclear catalysis was not as high as that of di-palladium catalysis. These calculation results were in good agreement with the experimental results.

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“…The use of microkinetic models has so far been rather scarce in computational homogeneous catalysis. The prominent reaction steps in a catalytic cycle can be often identified from experimental data, however, there are well-documented examples wherein key short-lived intermediates were identified using computational methods. − The most practical interpretations have been conducted by the direct analysis of the potential energy surface to determine the most favorable reaction pathway based on the activation energy of the elementary steps. − In these cases, microkinetic modeling can be used to understand intricacies of a complicated reaction mechanism. Microkinetic modeling is an indispensable tool in studying large reaction mechanisms where the conventional analysis becomes difficult due to the size of the reaction network.…”

Section: Microkinetic Models In Homogeneous Catalysismentioning

confidence: 99%

Microkinetic Modeling: A Tool for Rational Catalyst Design

2020

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The design of heterogeneous catalysts relies on understanding the fundamental surface kinetics that controls catalyst performance, and microkinetic modeling is a tool that can help the researcher in streamlining the process of catalyst design. Microkinetic modeling is used to identify critical reaction intermediates and rate-determining elementary reactions, thereby providing vital information for designing an improved catalyst. In this review, we summarize general procedures for developing microkinetic models using reaction kinetics parameters obtained from experimental data, theoretical correlations, and quantum chemical calculations. We examine the methods required to ensure the thermodynamic consistency of the microkinetic model. We describe procedures required for parameter adjustments to account for the heterogeneity of the catalyst and the inherent errors in parameter estimation. We discuss the analysis of microkinetic models to determine the rate-determining reactions using the degree of rate control and reversibility of each elementary reaction. We introduce incorporation of Brønsted–Evans–Polanyi relations and scaling relations in microkinetic models and the effects of these relations on catalytic performance and formation of volcano curves are discussed. We review the analysis of reaction schemes in terms of the maximum rate of elementary reactions, and we outline a procedure to identify kinetically significant transition states and adsorbed intermediates. We explore the application of generalized rate expressions for the prediction of optimal binding energies of important surface intermediates and to estimate the extent of potential rate improvement. We also explore the application of microkinetic modeling in homogeneous catalysis, electro-catalysis, and transient reaction kinetics. We conclude by highlighting the challenges and opportunities in the application of microkinetic modeling for catalyst design.

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Key Mechanistic Features in Palladium-Catalyzed Methylcyclopropanation of Norbornenes With Vinyl Bromides: Insights From DFT Calculations

Cited by 5 publications

References 82 publications

Unusual Ring Opening of Bicyclic Terpenes During Pd‐Catalyzed Coupling with Aromatic Halides

Unusual Ring Opening of Bicyclic Terpenes During Pd‐Catalyzed Coupling with Aromatic Halides

DFT Study on Dinuclear Palladium Complex Catalyzed Pyrrole Formation From tert‐Butyl Isocyanide and Alkynes

Microkinetic Modeling: A Tool for Rational Catalyst Design

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