Elucidating the Origin of Regioselectivity in Palladium-Catalyzed Aromatic Fluorination: Mechanistic Investigation and Microkinetic Analysis

Pliego, Josefredo R.

doi:10.1007/s10562-024-04706-x

Catal Lett

2024

DOI: 10.1007/s10562-024-04706-x

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Elucidating the Origin of Regioselectivity in Palladium-Catalyzed Aromatic Fluorination: Mechanistic Investigation and Microkinetic Analysis

Josefredo R. Pliego

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2024

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Cited by 2 publications

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Theoretical design of new ligands to boost reaction rate and selectivity in palladium‐catalyzed aromatic fluorination

Pliego

2024

J Comput Chem

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The development of palladium‐catalyzed fluorination with biaryl monophosphine ligands has faced two important problems that limit its application for bromoarenes: the formation of regioisomers and insufficient catalysis for heteroaryl substrates as bromothiophene derivatives. Overcoming these problems requires more ligand design. In this work, reliable theoretical calculations were used to elucidate important ligand features necessary for achieving more rate acceleration and selectivity. These features include increasing the ligand‐substrate repulsion and creating a negative charge in the space around the fluoride ion bonded to the palladium. The investigated L5 ligand presents these features, and the calculations predict that this ligand completely suppresses the regioisomer formation in the difficult case of 4‐bromoanisole. In addition, the free energy barriers are decreased by 2–3 kcal mol−1 in comparison with the catalysis involving the AlPhos ligand. Thus, the present study points out a direction for new developments in palladium‐catalyzed fluorination.

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Theoretical design of new ligands to boost reaction rate and selectivity in palladium‐catalyzed aromatic fluorination

Pliego

2024

J Comput Chem

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Effects of Hydrogen Bonding Solvation by Diverse Fluorinated Bulky Alcohols on the Reaction Rate and Selectivity in Crown Ether Mediated Nucleophilic Fluorination in an Aprotic Solvent

Ávila,

de Almeida,

Valle

et al. 2024

ACS Org. Inorg. Au

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Elucidating the Origin of Regioselectivity in Palladium-Catalyzed Aromatic Fluorination: Mechanistic Investigation and Microkinetic Analysis

Cited by 2 publications

References 63 publications

Theoretical design of new ligands to boost reaction rate and selectivity in palladium‐catalyzed aromatic fluorination

Theoretical design of new ligands to boost reaction rate and selectivity in palladium‐catalyzed aromatic fluorination

Effects of Hydrogen Bonding Solvation by Diverse Fluorinated Bulky Alcohols on the Reaction Rate and Selectivity in Crown Ether Mediated Nucleophilic Fluorination in an Aprotic Solvent

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