Organopalladium Catalysis as a Proving Ground for Data-Rich Approaches to Reaction Development and Quantitative Predictions

Lu, Jingru; Leitch, David C.

doi:10.1021/acscatal.3c03864

Cited by 2 publications

(1 citation statement)

References 134 publications

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“…Generally, a palladium-catalyzed reaction may experience variable valence characteristics due to different reaction conditions, including the following: Pd(0) → Pd(II) → Pd(0), Pd(0) → Pd(II) → Pd(IV), Pd(II) → Pd(0) → Pd(II) or Pd(II) → Pd(IV) → Pd(II) as well as remaining Pd(II)-only throughout. − A few reports based on density functional theory (DFT) studies on the formation of some phenanthrene derivatives are available and have explained the corresponding reaction mechanism at the microscopic level. − However, to the best of our knowledge, only a few computational works focused on the palladium-catalyzed syntheses of phenanthrenes from two different aryl halides are available. According to Cárdenas’s report on the palladium-catalyzed domino reaction, the optimal pathway leading to C(sp 2 )–C(sp 2 ) bonding proceeds through a Pd(II)–Pd(II) transmetalation process.…”

Section: Introductionmentioning

confidence: 99%

Palladium-Catalyzed Sequential Cross-Coupling/Annulation of ortho-Vinyl Bromobenzene with Aryl Bromide: Bimetallic Pathway versus Pd(II)–Pd(IV) Pathway: A DFT Investigation

Zhang,

Shi,

Tan

et al. 2024

J. Org. Chem.

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The palladium-catalyzed sequential cross-coupling/ annulation of ortho-vinyl bromobenzenes with aryl bromides generating phenanthrenes was characterized by density functional theory (DFT). The Pd(II)−Pd(IV) pathway (Path V) is shown to be less probable than the bimetallic pathway (Path I), the latter proceeding via the following six steps: oxidative addition, vinyl-C(sp 2 )-H activation, Pd(II)−Pd(II) transmetalation, C−C coupling, aryl-C(sp 2 )-H activation, and reductive elimination. The aryl-C(sp 2 )-H activation process acts as the rate-determining step (RDS) of the entire chemical transformation, with an activation free energy barrier of ca. 27.4−28.8 kcal•mol −1 , in good agreement with the corresponding experimental data (phenanthrenes' yields of ca. 65−90% at 130 °C after 5 h of reaction). The K 2 CO 3 additive effectively reduces the activation free energy barrier of the RDS through direct participation in the reaction while preferentially modulating the charge distributions and increasing the stability of corresponding intermediates and complexes along the reaction path. Furthermore, bonding and electronic structure analyses of the key structures indicate that the chemo-and regioselectivities of the reaction are strongly influenced by both electronic effects and steric hindrance.

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Section: Introductionmentioning

confidence: 99%

Palladium-Catalyzed Sequential Cross-Coupling/Annulation of ortho-Vinyl Bromobenzene with Aryl Bromide: Bimetallic Pathway versus Pd(II)–Pd(IV) Pathway: A DFT Investigation

Zhang,

Shi,

Tan

et al. 2024

J. Org. Chem.

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Data-Driven Insights into the Transition-Metal-Catalyzed Asymmetric Hydrogenation of Olefins

Singh,

Hernández-Lobato

2024

J. Org. Chem.

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The transition-metal-catalyzed asymmetric hydrogenation of olefins is one of the key transformations with great utility in various industrial applications. The field has been dominated by the use of noble metal catalysts, such as iridium and rhodium. The reactions with the earth-abundant cobalt metal have increased only in recent years. In this work, we analyze the large amount of literature data available on iridium-and rhodiumcatalyzed asymmetric hydrogenation. The limited data on reactions using Co catalysts are then examined in the context of Ir and Rh to obtain a better understanding of the reactivity pattern. A detailed data-driven study of the types of olefins, ligands, and reaction conditions such as solvent, temperature, and pressure is carried out. Our analysis provides an understanding of the literature trends and demonstrates that only a few olefin−ligand combinations or reaction conditions are frequently used. The knowledge of this bias in the literature data toward a certain group of substrates or reaction conditions can be useful for practitioners to design new reaction data sets that are suitable to obtain meaningful predictions from machine-learning models.

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Organopalladium Catalysis as a Proving Ground for Data-Rich Approaches to Reaction Development and Quantitative Predictions

Cited by 2 publications

References 134 publications

Palladium-Catalyzed Sequential Cross-Coupling/Annulation of ortho-Vinyl Bromobenzene with Aryl Bromide: Bimetallic Pathway versus Pd(II)–Pd(IV) Pathway: A DFT Investigation

Palladium-Catalyzed Sequential Cross-Coupling/Annulation of ortho-Vinyl Bromobenzene with Aryl Bromide: Bimetallic Pathway versus Pd(II)–Pd(IV) Pathway: A DFT Investigation

Data-Driven Insights into the Transition-Metal-Catalyzed Asymmetric Hydrogenation of Olefins

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