4.6 Review

Ionic Liquids as Organocatalysts for Nucleophilic Fluorination: Concepts and Perspectives

相关参考文献

注意:仅列出部分参考文献,下载原文获取全部文献信息。
Review Chemistry, Organic

Facile and Environment-friendly Fluorinations using Ionic Liquids

Komal Jakhar

Summary: Recent innovations in fluorination techniques highlight the significant role of ionic liquids in fluorotransformations, such as the use of tagged ionic liquids in nucleophilic fluorinations, ionic liquid assisted biological fluorination, enantioselective fluorinations using chiral electrophilic reagents in ionic liquid media, task-specific ionic liquids in electrochemical fluorinations with mediators, and ionic liquid promoted synthesis of medicinally important fluorinated heteroaromatics and radiopharmaceuticals.

CURRENT ORGANIC SYNTHESIS (2022)

Article Chemistry, Organic

Diaryliodoniums as Hybrid Hydrogen- and Halogen-Bond-Donating Organocatalysts for the Groebke-Blackburn-Bienayme Reaction

Mikhail Il'in et al.

Summary: Dibenziodolium and diphenyliodonium triflates have been found to exhibit high catalytic activity in a multicomponent reaction. The study also reveals that the hydrogen atoms adjacent to the iodine atom play a dual role in forming noncovalent bonds with the substrate and increasing the electrostatic potential at the iodine atom. The higher catalytic activity of Dibenziodolium triflate can be explained by the additional energy required for the rotation of the phenyl ring in the diphenyliodonium cation during substrate ligation.

JOURNAL OF ORGANIC CHEMISTRY (2022)

Article Biochemistry & Molecular Biology

Nucleophilic Radiofluorination Using Tri-tert-Butanol Ammonium as a Bifunctional Organocatalyst: Mechanism and Energetics

Young-Ho Oh et al.

Summary: In this paper, we present a quantum chemical analysis of the F-18-fluorination of 1,3-ditosylpropane, focusing on the role of -OH functional groups in the reaction. We found that the counter-cation TBMA(+) acts as a bifunctional promoter in the reaction process.

MOLECULES (2022)

Article Chemistry, Multidisciplinary

Enhancement of SNAr reactions by CH3SO3- ionic liquid and organic solvent dimethylformamide as bifunctional organocatalysts: A mechanistic study

Young-Ho Oh et al.

Summary: The quantum chemical analysis presented here sheds light on the mechanism of the SNAr reaction of p-fluoronitrobenzene and p-anisidine promoted by [C(4)C(1)im][CH3SO3] and DMF. The study suggests that [C(4)C(1)im](+) aids in detachment of the fluoride group, while [CH3SO3](-) provides partial negative charge to the nucleophile -NH2, enhancing reactivity. Furthermore, the moderate yield in DMF can be explained by considering the solvent molecule as a bifunctional organocatalyst, and the calculated Gibbs free energies of activation are in excellent agreement with experimental observations.

BULLETIN OF THE KOREAN CHEMICAL SOCIETY (2022)

Article Chemistry, Physical

Comparison between Ab Initio Molecular Dynamics and OPLS-Based Force Fields for Ionic Liquid Solvent Organization

Kun Yue et al.

Summary: In this study, the ability of OPLS to reproduce an IL solvent structure was examined using ab initio molecular dynamics simulations. The comparisons between AIMD and OPLS FFs showed that the OPLS-VSIL FF can accurately reproduce interaction distances and provide insights into the different short-and long-range structure patterns of ILs.

JOURNAL OF PHYSICAL CHEMISTRY B (2022)

Article Chemistry, Medicinal

18F-Fluorination Using Tri-Tert-Butanol Ammonium Iodide as Phase-Transfer Catalyst: An Alternative Minimalist Approach

Sandip S. Shinde et al.

Summary: This study developed TBMA-I as a PTC for F-18-fluorination reactions, demonstrating its favorable elution efficiency and potential application in labeling reactions.

PHARMACEUTICALS (2021)

Article Chemistry, Multidisciplinary

Hypervalent Iodonium Zwitterions and Nucleophilic Aromatic Substitution: A Multiple-Step Experiment in Organic Chemistry

Jianwei Han et al.

Summary: Iodonium zwitterions are hypervalent iodine compounds with a positive charge compensated by a negative charge within the same molecule, allowing for concerted nucleophilic aromatic substitutions and rearrangement reactions. The laboratory experiments aim to provide insight into the concepts of nucleophilic aromatic substitutions and iodonium zwitterions, as well as to demonstrate important topics and experimental skills in organic chemistry. Additionally, students are taught analytical techniques such as NMR spectroscopy, mass spectrometry, and X-ray diffraction.

JOURNAL OF CHEMICAL EDUCATION (2021)

Article Chemistry, Multidisciplinary

Hydrogen Bonding in SN2 Reactions Promoted or Inhibited by Ionic Liquids: Effects of Side Chain

Young-Ho Oh et al.

Summary: The study demonstrates that [hexaEGmim][PF6] suppresses S(N)2 fluorination by positioning the nucleophile F- far from the electropositive carbon atom through hydrogen bonding, while [bmim][PF6] facilitates the reaction by bringing F- in close proximity to the carbon atom for nucleophilic attack. The use of ionic interactions and hydrogen bonding in controlling chemical reactions for designing efficient organocatalysts is illustrated.

BULLETIN OF THE KOREAN CHEMICAL SOCIETY (2021)

Article Biochemistry & Molecular Biology

Origin of Salt Effects in SN2 Fluorination Using KF Promoted by Ionic Liquids: Quantum Chemical Analysis

Young-Ho Oh et al.

Summary: The study presents a quantum chemical analysis of the role of KF in two different ionic liquids, elucidating the promoting capacity of KF in [bmim]PF6 and the impact of adding KPF6 on the reaction rate acceleration. The observed rate enhancement is attributed to the combined effect of KF and KPF6, which decreases the Gibbs free energy of activation and further activates S(N)2 fluorination.

MOLECULES (2021)

Article Chemistry, Organic

Preparation and Synthetic Applicability of Imidazole-Containing Cyclic Iodonium Salts

Nikita S. Antonkin et al.

Summary: A novel method has been developed for the synthesis of imidazole-substituted cyclic iodonium salts via oxidative cyclization reaction of 1-phenyl-5-iodoimidazole. The newly synthesized compounds can readily react with elemental sulfur to afford benzo[5,1-b]imidazothiazoles in good yields. Single-crystal X-ray diffractometry confirmed the structure of the new polycyclic heteroarenes, revealing the characteristic features for cyclic iodonium salts.

JOURNAL OF ORGANIC CHEMISTRY (2021)

Review Chemistry, Multidisciplinary

Toward the Proactive Design of Sustainable Chemicals: Ionic Liquids as a Prime Example

Stephan Beil et al.

Summary: The tailorable properties of ionic liquids drive their implementation into various technologies, with a focus on environmental sustainability. To design more sustainable ILs, selection of beneficial precursors, considering technical properties, and evaluating environmental impacts are crucial. Understanding structure-activity relationships and mechanisms at a molecular level is important for rationalizing design criteria.

CHEMICAL REVIEWS (2021)

Article Chemistry, Organic

In Situ Anodically Oxidized BMIm-BF4: A Safe and Recyclable BF3 Source

Martina Bortolami et al.

Summary: The anodic oxidation of 1-butyl-3-methylimidazolium tetrafluoroborate efficiently generates BF3 from BF4-, which can be used in a variety of reactions with similar or improved results compared to traditional BF3-Et2O methods. The developed method allows in situ generation of BF3, uses electrons as the only redox reagent, and enables recycling of BMIm-BF4 for multiple runs, making it environmentally friendly.

JOURNAL OF ORGANIC CHEMISTRY (2021)

Article Chemistry, Organic

Predicting the catalytic activity of azolium-based halogen bond donors: an experimentally-verified theoretical study

Alexandra A. Sysoeva et al.

Summary: This study demonstrated the successful application of electrostatic surface potential distribution analysis in assessing the catalytic activity of azolium-based halogen bond donors, revealing a strong correlation between the positive electrostatic potential of the sigma-hole on the halogen atom and the Gibbs free energy of activation of the model reactions. The research confirmed the predictive ability of the applied approach and identified that the catalytic activity of azolium-based halogen bond donors is primarily governed by the structure of the azolium cycle, with limited impact from substituents on the heterocycle. Ultimately, the study identified four promising azolium halogen bond donors expected to exhibit high catalytic activity.

ORGANIC & BIOMOLECULAR CHEMISTRY (2021)

Article Chemistry, Multidisciplinary

Iodonium salts as efficient iodine(iii)-based noncovalent organocatalysts for Knorr-type reactions

Sevilya N. Yunusova et al.

Summary: Hypervalent iodine(iii)-derivatives have higher catalytic activity than other aliphatic and aromatic iodine(i)- or bromine(i)-containing substrates for a Knorr-type reaction, with dibenziodolium triflate showing the highest activity for generating N-acyl pyrazoles. The catalytic activity of iodine(iii) is attributed to its binding with a ketone, as indicated by H-1 NMR titration data and DFT calculations.

RSC ADVANCES (2021)

Review Biochemistry & Molecular Biology

Harnessing Ionic Interactions and Hydrogen Bonding for Nucleophilic Fluorination

Young-Ho Oh et al.

MOLECULES (2020)

Article Chemistry, Organic

Hypervalent Iodine(III)-Mediated Tosyloxylation of 4-Hydroxycoumarins

Bowen Xu et al.

JOURNAL OF ORGANIC CHEMISTRY (2019)

Article Chemistry, Physical

Virtual Site OPLS Force Field for Imidazolium-Based Ionic Liquids

Brian Doherty et al.

JOURNAL OF PHYSICAL CHEMISTRY B (2018)

Article Biochemical Research Methods

Improved, one-pot synthesis of 6-[18F]fluorodopamine and quality control testing for use in patients with neuroblastoma

Amy L. Vavere et al.

JOURNAL OF LABELLED COMPOUNDS & RADIOPHARMACEUTICALS (2018)

Article Chemistry, Physical

Revisiting OPLS Force Field Parameters for Ionic Liquid Simulations

Brian Doherty et al.

JOURNAL OF CHEMICAL THEORY AND COMPUTATION (2017)

Review Chemistry, Multidisciplinary

Advances in Synthetic Applications of Hypervalent Iodine Compounds

Akira Yoshimura et al.

CHEMICAL REVIEWS (2016)

Article Multidisciplinary Sciences

Concerted nucleophilic aromatic substitution with 19F- and 18F-

Constanze N. N. Eumann et al.

NATURE (2016)

Review Biochemical Research Methods

[18F]6-fluoro-3,4-dihydroxy-L-phenylalanine - recent modern syntheses for an elusive radiotracer

Richard Edwards et al.

JOURNAL OF LABELLED COMPOUNDS & RADIOPHARMACEUTICALS (2015)

Article Chemistry, Organic

Convenient Synthesis of Diaryliodonium Salts for the Production of [18F]F-DOPA

Richard Edwards et al.

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY (2015)

Article Chemistry, Physical

Ionic Liquid Effects on Nucleophilic Aromatic Substitution Reactions from QM/MM Simulations

Caley Allen et al.

JOURNAL OF PHYSICAL CHEMISTRY B (2015)

Article Chemistry, Physical

Simulating Chemical Reactions in Ionic Liquids Using QM/MM Methodology

Orlando Acevedo

JOURNAL OF PHYSICAL CHEMISTRY A (2014)

Article Chemistry, Organic

Solvent free nucleophilic introduction of fluorine with [bmim][F]

Sebastien Bouvet et al.

TETRAHEDRON LETTERS (2014)

Review Chemistry, Applied

Ionic Liquids in Pharmaceutical Applications

I. M. Marrucho et al.

ANNUAL REVIEW OF CHEMICAL AND BIOMOLECULAR ENGINEERING, VOL 5 (2014)

Article Chemistry, Organic

Hypervalent Iodine Mediated para-Selective Fluorination of Anilides

Tian Tian et al.

JOURNAL OF ORGANIC CHEMISTRY (2013)

Review Chemistry, Multidisciplinary

Room-Temperature Ionic Liquids: Solvents for Synthesis and Catalysis. 2

Jason P. Hallett et al.

CHEMICAL REVIEWS (2011)

Article Chemistry, Physical

Hydrogen Evolution from Formic Acid in an Ionic Liquid Solvent: A Mechanistic Study by ab Initio Molecular Dynamics

B. L. Bhargava et al.

JOURNAL OF PHYSICAL CHEMISTRY B (2011)

Article Chemistry, Organic

S(N)2 Fluorination reactions in ionic liquids: a mechanistic study towards solvent engineering

Young-Ho Oh et al.

ORGANIC & BIOMOLECULAR CHEMISTRY (2011)

Article Chemistry, Applied

Recyclable Polymer-Supported Iodobenzene-Mediated Electrocatalytic Fluorination in Ionic Liquid

Takahiro Sawamura et al.

ADVANCED SYNTHESIS & CATALYSIS (2010)

Article Chemistry, Multidisciplinary

On Catalysis by Ionic Liquids

Asit K. Chakraborti et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2009)

Article Chemistry, Organic

Ionic liquids/[bmim][N3] mixtures:: Promising media for the synthesis of aryl azides by SNAr

Francesca D'Anna et al.

JOURNAL OF ORGANIC CHEMISTRY (2008)

Article Chemistry, Physical

Facile SN2 reaction in protic solvent:: Quantum chemical analysis

Young-Ho Oh et al.

JOURNAL OF PHYSICAL CHEMISTRY A (2007)

Review Chemistry, Multidisciplinary

Catalysis in ionic liquids

Vasile I. Parvulescu et al.

CHEMICAL REVIEWS (2007)

Article Chemistry, Physical

Elucidation of rate variations for a Diels-Alder reaction in ionic liquids from QM/MM simulations

Orlando Acevedo et al.

JOURNAL OF CHEMICAL THEORY AND COMPUTATION (2007)

Review Chemistry, Multidisciplinary

Biocatalysis in ionic liquids

Fred van Rantwijk et al.

CHEMICAL REVIEWS (2007)

Article Chemistry, Multidisciplinary

A new class of SN2 reactions catalyzed by protic solvents:: Facile fluorination for isotopic labeling of diagnostic molecules

Dong Wook Kim et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2006)

Article Chemistry, Applied

Activation of nucleophilic fluorination by salts in ionic liquids and in sulfolane

Stephane Anguille et al.

ADVANCED SYNTHESIS & CATALYSIS (2006)

Article Chemistry, Inorganic & Nuclear

Friedel-Crafts acylation reactions in pyridinium based ionic liquids

Y Xiao et al.

JOURNAL OF ORGANOMETALLIC CHEMISTRY (2005)

Article Chemistry, Multidisciplinary

Polymer-supported ionic liquids: Imidazolium salts as catalysts for nucleophilic substitution reactions including fluorinations

DW Kim et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2004)

Article Chemistry, Organic

Significantly enhanced reactivities of the nucleophilic substitution reactions in ionic liquid

DW Kim et al.

JOURNAL OF ORGANIC CHEMISTRY (2003)

Article Radiology, Nuclear Medicine & Medical Imaging

A new nucleophilic fluorine-18 labeling method for aliphatic mesylates: Reaction in ionic liquids shows tolerance for water

DW Kim et al.

NUCLEAR MEDICINE AND BIOLOGY (2003)

Review Biochemical Research Methods

Radiohalogen incorporation into organic systems

R Bolton

JOURNAL OF LABELLED COMPOUNDS & RADIOPHARMACEUTICALS (2002)

Article Chemistry, Physical

The cluster-continuum model for the calculation of the solvation free energy of ionic species

JR Pliego et al.

JOURNAL OF PHYSICAL CHEMISTRY A (2001)

Article Chemistry, Multidisciplinary

Cycloaddition of carbon dioxide to propylene oxide catalyzed by ionic liquids

JJ Peng et al.

NEW JOURNAL OF CHEMISTRY (2001)