Theoretical study of the mechanism of palladium-catalyzed hydroaminocarbonylation of styrene with ammonium chloride

Wei, Wen-mei; Dong, Fengqi; Zheng, Ren-Hui; Li, Yanying; Zhao, Tingting; Fang, Weijun; Qin, Yide

doi:10.1016/j.comptc.2020.113040

Cited by 5 publications

(3 citation statements)

References 73 publications

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“…This phenomenon has appeared in many literature studies when scientists investigated molecular transition states. 47 , 52 − 55 The reason may be that the reaction energy barrier of the transition state is very small.…”

Section: Results and Discussionmentioning

confidence: 99%

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Theoretical Study on the Mechanism of the Acylate Reaction of β-Lactamase

Wei

Zheng

et al. 2021

ACS Omega

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Using density functional theory and a cluster approach, we study the reaction potential surface and compute Gibbs free energies for the acylate reaction of β-lactamase with penicillin G, where the solvent effect is important and taken into consideration. Two reaction paths are investigated: one is a multi-step process with a rate-limit energy barrier of 19.1 kcal/mol, which is relatively small, and the reaction can easily occur; the other is a one-step process with a barrier of 45.0 kcal/mol, which is large and thus makes the reaction hard to occur. The reason why the two paths have different barriers is explained.

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Section: Results and Discussionmentioning

confidence: 99%

“…The M08HX functional can investigate the intermolecular and intramolecular nonbonding interactions well . In our previous investigations, the M08HX functional is utilized to study polypeptides and organometallic compounds, and good results are obtained. − …”

Section: Computational Detailsmentioning

confidence: 99%

Theoretical Study on the Mechanism of the Acylate Reaction of β-Lactamase

Wei

Zheng

et al. 2021

ACS Omega

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“…Very recently, Qin 16 and Liu 17 successively reported density functional theory (DFT) studies on the Pd-catalyzed HAC of styrene with CO and NH 4 Cl. Qin's study used Pd(H)Cl as the catalyst and ignored the effect of phosphine ligands.…”

Section: Introductionmentioning

confidence: 99%

Double-Regiodetermining-Stages Mechanistic Model Explaining the Regioselectivity of Pd-Catalyzed Hydroaminocarbonylation of Alkenes with Carbon Monoxide and Ammonium Chloride

Liu

et al. 2021

J. Org. Chem.

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Pd-catalyzed hydroaminocarbonylation (HAC) of alkenes with CO and NH 4 Cl enables atom-economic and regiodivergent synthesis of primary amides, but the origin of regioselectivity was incorrectly interpreted in previous computational studies. A density functional theory study was performed herein to investigate the mechanism. Different from the previous proposals, both alkene insertion and aminolysis were found to be potential regioselectivity-determining stages. In the alkene insertion stage, 2,1insertion is generally faster than 1,2-insertion irrespective of neutral or cationic pathways for both P( t Bu) 3 and xantphos. Such selectivity results from the unconventional proton-like hydrogen of the Pd−H bond in alkene insertion transition states. For less bulky alkenes, aminolysis with P( t Bu) 3 shows low selectivity, while linear selectivity dominates in this stage with xantphos due to a stronger repulsion between xantphos and branched acyl ligands. It was further revealed that the less-mentioned CO concentration and solvents also influence the regioselectivity by adjusting the relative feasibilities of CO-involved steps and NH 3 release from ammonium chloride, respectively. The presented double-regiodeterminingstages mechanistic model associated with the effects of ligands, CO concentration, and solvents well reproduced the experimental selectivity to prove its validity and illuminated new perspectives for the regioselectivity control of HAC reactions.

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Employing Ammonia for Diverse Amination Reactions: Recent Developments of Abundantly Available and Challenging Nitrogen Sources

et al. 2022

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Ammonia is the simplest molecule for the installation of nitrogen atom in organic compounds. It is abundantly available, economic and highly attractive from the point of atom economy for its use in organic synthesis, however, an highly challenging task for accessing the nitrogenous scaffolds through NÀ H activation of ammonia. With the advancement of synthetic procedures, scientific community continually developing excellent reactions employing ammonia as a source of nitrogen for various types of amination reactions and accomplishing the synthesis of nitrogenous compounds. This Review provides recent developments in amination reactions employing ammonia as a nitrogen source at a single platform.

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Theoretical study of the mechanism of palladium-catalyzed hydroaminocarbonylation of styrene with ammonium chloride

Cited by 5 publications

References 73 publications

Theoretical Study on the Mechanism of the Acylate Reaction of β-Lactamase

Theoretical Study on the Mechanism of the Acylate Reaction of β-Lactamase

Double-Regiodetermining-Stages Mechanistic Model Explaining the Regioselectivity of Pd-Catalyzed Hydroaminocarbonylation of Alkenes with Carbon Monoxide and Ammonium Chloride

Employing Ammonia for Diverse Amination Reactions: Recent Developments of Abundantly Available and Challenging Nitrogen Sources

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