The mechanism of the Pd-catalyzed formation of coumarins: a theoretical study

文献情報

出版日 2014-11-12

DOI 10.1039/C4CP03418J

インパクトファクター 3.676

著者

S. Nedd

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要旨

The mechanism of the formation of coumarins via the Pd-catalyzed intramolecular hydroarylation of the C–C triple bond is elucidated computationally, in corroboration with experimental data. It is shown that the reaction follows the concerted metalation–deprotonation (CMD) mechanism. The typically suspected mechanisms of ambiphilic metal ligand activation (AMLA), electrophilic aromatic substitution (EAS), and oxidative addition (OA) are suggested to be non-competitive, based on predicted conformations and energetics. Two forms of the Pd catalysts are used: Pd(OAc)2, and Pd(TFA)2. The predicted activation free energy barrier for the TFA-based catalyst is lower, both in the gas phase and in the CH2Cl2 solvent, in agreement with the experimental observations. Adding electron-withdrawing groups to the catalyst assists the first and rate-limiting step of the reaction, the deprotonation of the aromatic ring, as understood through charge analysis.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

The mechanism of the Pd-catalyzed formation of coumarins: a theoretical study

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Physical Chemistry Chemical Physics

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