Chemoselectivity in Gold(I)-Catalyzed Propargyl Ester Reactions: Insights From DFT Calculations

Sun, Qing; Pan, Hong; Wei, Dongdong; Wu, Anan; Kai, Tetsuya; Lü, Xin

doi:10.3389/fchem.2019.00609

Cited by 5 publications

(3 citation statements)

References 63 publications

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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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Section: Microkinetic Models In Homogeneous Catalysismentioning

confidence: 99%

Microkinetic Modeling: A Tool for Rational Catalyst Design

2020

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“…9 This combination of functional and basis sets has been frequently used in mechanistic investigations on Au-catalyzed organic transformations. 10 Frequency calculations at the same level were performed to confirm each stationary point to be either a local minimum or a transition state (TS). The transition states were verified using intrinsic reaction coordinate (IRC) 11 calculations.…”

Section: Introductionmentioning

confidence: 99%

Insights into the gold(i)-catalyzed intermolecular annulations of alkynes with N-allenamides: a mechanistic DFT study

et al. 2022

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“…Primeiramente, os cálculos foram realizados com apenas um funcional, o B3LYP. Outro funcional muito recorrente na catálise por ouro é o M06 36,64,146. Dessa forma, seria interessante fazer o benchmark entre os dois.…”

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Estudo mecanístico da reação de hidrocloração de alquinos não ativados: perspectiva com e sem complexos de ouro(I)

Quilici¹

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The homogeneous catalysis by gold(I) complexes generally acts in an alkyne as substrate and occurs under a nucleophilic addition, forming the anti alkene as the product. First, a pre-catalysis step with silver salts is done, acting on LAuCl specie (where L is an organic ligand), which generates LAu + catalyst when breaking Au-Cl bond. Recently, the hydrochlorination reaction of alkynes catalyzed by gold(I) complexes was reported, under room temperature and open air, without the pre-catalysis step and possibly maintaining the Au-Cl bond all over the reaction course. This could be feasible by hydrogen bonds between HCl, HFIP (hexafluoroisopropanol) molecules and the inactive catalyst, LAuCl. Later, a new study, using a bromoalkyne as substrate, showed to be possible the alkene obtainment as a syn product, but without the presence of gold catalyst (or any other one). So, the gold presence leads the regioselectivity of the hydrochlorination of alkynes, resulting only the anti product. With Density Functional Theory (DFT), the reaction pathways were studied, with gold (LAu + ) and without it, aiming to understand the main aspects that drive the regioselectivity in the alkynes hydrochlorination reaction. The activation of LAuCl catalyst was studied either. In the regioselectivity case, the steric hindrance promoted by bromine atom guides the major formation of syn product, which transition state is 3 kcal.mol -1 more stable than the anti one. In the gold reaction, the metal is the responsible one for steric hindrance to the nucleophile, directing it to the anti position. Finally, in the LAuCl catalyzed reaction, HFIP molecule seems to be decisive to initiate the catalyst activation, by its interaction with the triple bond.

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Chemoselectivity in Gold(I)-Catalyzed Propargyl Ester Reactions: Insights From DFT Calculations

Cited by 5 publications

References 63 publications

Microkinetic Modeling: A Tool for Rational Catalyst Design

Microkinetic Modeling: A Tool for Rational Catalyst Design

Insights into the gold(i)-catalyzed intermolecular annulations of alkynes with N-allenamides: a mechanistic DFT study

Estudo mecanístico da reação de hidrocloração de alquinos não ativados: perspectiva com e sem complexos de ouro(I)

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