Acid and Base Water Coexists in a Micro‐Structured Ionic Liquid and Catalyzes Organic Reactions in One‐Pot

Leyva‐Pérez, Antonio; Bilanin, Cristina; Bacic, Matea; Greco, Rossella

doi:10.1002/cctc.202200557

Cited by 4 publications

(5 citation statements)

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“… [31] In order to obtain the enyne compounds in a more sustainable and reusable system, we have performed the cascade reaction in ionic liquids. In our group, we have previously optimized other catalytic reactions in ionic liquids,[ 32 , 33 ] including cascade processes. [33] Here, we tested different ionic liquids, and it was found that [bmim][PF 6 ], [bmim][BF 4 ] and [bmim][OTf] are all suitable for the reaction, to give yields of 3 a >90 % (Figure S7).…”

Section: Resultsmentioning

confidence: 99%

“…In our group, we have previously optimized other catalytic reactions in ionic liquids,[ 32 , 33 ] including cascade processes. [33] Here, we tested different ionic liquids, and it was found that [bmim][PF 6 ], [bmim][BF 4 ] and [bmim][OTf] are all suitable for the reaction, to give yields of 3 a >90 % (Figure S7). The ionic liquids with Cl − as a counteranion (entries 3 and 6 in Figure S7) where discarded because they formed the Cl‐substituted Sonogashira intermediate, after substitution of the Br by the Cl atom, hampering the elimination step.…”

Section: Resultsmentioning

confidence: 99%

“…the cascade reaction in ionic liquids. In our group, we have previously optimized other catalytic reactions in ionic liquids, [32,33] including cascade processes. [33] Here, we tested different ionic liquids, and it was found that [bmim][PF 6 ],…”

Section: Chemistry-a European Journalmentioning

confidence: 99%

“…Ionic liquids are suitable and recoverable solvents for different organic reactions, [32] including Sonogashira cross‐coupling reactions,[ 33 , 34 , 35 , 36 ] and allow the easy reuse of catalytic metal species after reaction. We will also show here that our synthetic methodology is compatible with the use of ionic liquid solvents, with the advantage of the reusability of the catalytic system.…”

Section: Introductionmentioning

confidence: 99%

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A Cascade Sonogashira Cross‐Coupling‐Substitution‐Elimination Reaction for the Synthesis of Linear Conjugated Dienynes

Lumbreras-Teijeiro

Bacic

Oliver‐Meseguer

et al. 2022

Chemistry A European J

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The engagement in tandem of well‐known organic reactions such as the Pd‐catalyzed Sonogashira cross‐coupling reaction, nucleophilic substitution and elimination reactions, enables the synthesis of otherwise difficult to obtain linear dienynes, in moderate to high yields. This retrosynthetic approach opens new ways to prepare highly conjugated alkenes and alkynes. Furthermore, ionic liquids are suitable solvents to perform the cascade reaction and recycle the metal catalysts.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Chemistry-a European Journalmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

A Cascade Sonogashira Cross‐Coupling‐Substitution‐Elimination Reaction for the Synthesis of Linear Conjugated Dienynes

Lumbreras-Teijeiro

Bacic

Oliver‐Meseguer

et al. 2022

Chemistry A European J

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“…Recently, the possibility of using the advantages of spatially localized reactions in media structured due to reagent-solvent interactions was reported, which opened new ways of developing chemistry in ordered liquids. [19][20][21] Seminal studies by A. Khlobystov, [22][23][24] C. Li, [25][26][27] L. Li, [28][29][30] and A. Corma [31][32][33] and their coworkers have shown the power of connecting molecular transformations and supramolecular/nanoscale properties of the environment. The transition from molecular to nanoand microscale in the study of chemical reactions in liquid media requires the use of specially designed experimental approaches.…”

Section: Introductionmentioning

confidence: 99%

An Unusual Microdomain Factor Controls Interaction of Organic Halides with the Palladium Phase and Influences Catalytic Activity in the Mizoroki‐Heck Reaction

Kashin

Prima

Arkhipova

et al. 2023

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In this work, using a combination of scanning and transmission electron microscopy (SEM and TEM), the transformations of palladium‐containing species in imidazolium ionic liquids in reaction mixtures of the Mizoroki‐Heck reaction and in related organic media are studied to understand a challenging question of the relative reactivity of organic halides as key substrates in modern catalytic technologies. The microscopy technique detects the formation of a stable nanosized palladium phase under the action of an aryl (Ar) halide capable of forming microcompartments in an ionic liquid. For the first time, the correlation between the reactivity of the aryl halide and the microdomain structure is observed: Ar‐I (well‐developed microdomains) > Ar‐Br (microphase present) > Ar‐Cl (minor amount of microphase). Previously, it is assumed that molecular level factors, namely, carbon‐halogen bond strength and the ease of bond breakage, are the sole factors determining the reactivity of aryl halides in catalytic transformations. The present work reports a new factor connected with the nature of the organic substrates used and their ability to form a microdomain structure and concentrate metallic species, highlighting the importance of considering both the molecular and microscale properties of the reaction mixtures.

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Revealing the Mechanism of Combining Best Properties of Homogeneous and Heterogeneous Catalysis in Hybrid Pd/NHC Systems

Prima,

Kulikovskaya,

Novikov

et al. 2024

Angewandte Chemie

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The formation of transient hybrid nanoscale metal species from homogeneous molecular precatalysts has been demonstrated by in situ NMR studies of catalytic reactions involving transition metals with N‐heterocyclic carbene ligands (M/NHC). These hybrid structures provide benefits of both molecular complexes and nanoparticles, enhancing the activity, selectivity, flexibility, and regulation of active species. However, they are challenging to identify experimentally due to the unsuitability of standard methods used for homogeneous or heterogeneous catalysis. Utilizing a sophisticated solid‐state NMR technique, we provide evidence for the formation of NHC‐ligated catalytically active Pd nanoparticles (PdNPs) from Pd/NHC complexes during catalysis. The coordination of NHCs via C(NHC)‐Pd bonding to the metal surface was first confirmed by observing the Knight shift in the 13C NMR spectrum of the frozen reaction mixture. Computational modeling revealed that as little as few NHC ligands are sufficient for complete ligation of the surface of the formed PdNPs. Catalytic experiments combined with in situ NMR studies confirmed the significant effect of surface covalently bound NHC ligands on the catalytic properties of the PdNPs formed by decomposition of the Pd/NHC complexes. This observation shows the crucial influence of NHC ligands on the activity and stability of nanoparticulate catalytic systems.

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Acid and Base Water Coexists in a Micro‐Structured Ionic Liquid and Catalyzes Organic Reactions in One‐Pot

Cited by 4 publications

References 46 publications

A Cascade Sonogashira Cross‐Coupling‐Substitution‐Elimination Reaction for the Synthesis of Linear Conjugated Dienynes

A Cascade Sonogashira Cross‐Coupling‐Substitution‐Elimination Reaction for the Synthesis of Linear Conjugated Dienynes

An Unusual Microdomain Factor Controls Interaction of Organic Halides with the Palladium Phase and Influences Catalytic Activity in the Mizoroki‐Heck Reaction

Revealing the Mechanism of Combining Best Properties of Homogeneous and Heterogeneous Catalysis in Hybrid Pd/NHC Systems

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