Synthesis of bis(polyfluoroalkylated)imidazolium salts as key intermediates for fluorous NHC ligands

Skalický, Martin; Rybáčková, Markéta; Kysilka, Ondřej; Kvı́čalová, Magdalena; Cvačka, Josef; Čejka, Jan; Kvı́čala, Jaroslav

doi:10.1016/j.jfluchem.2009.07.015

Cited by 43 publications

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References 33 publications

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“…The missing spectroscopic data are disclosed here. 1-(1H,1H,2H,2H-Perfluorodecyl)imidazole [18] was prepared by a published method. Reference ILs 1-butyl-2,3-dimethyl-imidazolium (BMMIm) Tf 2 N and 1-ethyl-3-methyl-imidazolium (EMIm) triflimides were purchased from IoLiTec, Germany.…”

Section: Methodsmentioning

confidence: 99%

“…In an attempt to obtain FILs with a polar functional group, 4-amino-1,2,4-triazolium salts 3 and 4 were synthesized, although in disappointing yield. Therefore, other polar group-bearing substituents, such as hydroxyethyl or diethylaminoethyl (Scheme 1), were introduced by quaternization of polyfluorodecyl-imidazole [18] to give 5a and 6a in good yields. Again, ion metathesis yielded liquid salts 5b and 6b.…”

Section: Synthetic Considerationsmentioning

confidence: 99%

“…Solubilities of fluorinated gases in ILs with non-fluorous cations were also determined [15]. Dedicated fluorous imidazolium salts [16] and the corresponding Pd-N-heterocyclic carbene (NHC) complexes [17,18] display unique mutual solubility patterns with fluoroorganic solvents. For an analogous series of 1,2,4-triazolium-based ILs, miscibility data have been reported only for common organic solvents [19,20].…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Sorption Analysis of Task-specific Fluorous Ionic Liquids

Adamer

Laus

Griesser

et al. 2013

Zeitschrift Für Naturforschung B

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Six 1-alkyl-4-tridecafluorooctyl-1,2,4-triazolium triflimides 2a-f and 4-amino-1-tridecafluorooctyl-1,2,4-triazolium triflimide (4) were prepared from the respective iodides 1a-f (1a, 2a: n-propyl; 1b, 2b: n-butyl; 1c, 2c: n-hexyl; 1d, 2d: n-heptyl; 1e, 2e: n-octyl; 1f, 2f: n-decyl) and iodide 3 by ion metathesis. Compounds 2a and 4 are liquid at room temperature. Two liquid fluorous imidazolium salts bearing functionalized polar substituents were synthesized in an analogous manner, namely 1-(2-(diethylamino)ethyl)-3-(heptadecafluorodecyl)imidazolium triflimide (5b) and 1-(2-hydroxyethyl)-3-(heptadecafluorodecyl)imidazolium triflimide (6b) from the respective bromides 5a and 6a. The bis(triflimide) 5c has a melting point slightly above room temperature. Three fluorous ionic liquids (ILs; 2a, 5b, and 6b) were subjected to vapor sorption analysis at 25 • C and exhibited dual affinity to water and, even much more pronounced, to methoxynonafluorobutane (hydrofluoroether HFE-7100). Thus, IL 6b absorbed 3.2 % (by weight) water and 200 % HFE, whereas ILs 2a and 5b absorbed 0.4 and 0.5 % water, but 300 and 1200 % HFE, respectively. Commercial 1-butyl-2,3-dimethyl-imidazolium triflimide and 1-ethyl-3-methyl-imidazolium triflimide were used as reference compounds and absorbed 0.9 and 2.2 % water, respectively, but only 17 % HFE.

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Section: Methodsmentioning

confidence: 99%

Section: Synthetic Considerationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis and Sorption Analysis of Task-specific Fluorous Ionic Liquids

Adamer

Laus

Griesser

et al. 2013

Zeitschrift Für Naturforschung B

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“…65 Aiming to use fluorous biphasic catalysis, the fluorous palladium-NHC complex 13 (Chart 2) was described and tested in the Suzuki-Miyaura and Heck coupling reactions. 66 Although the catalyst performed well in both reactions, it could not be recycled using the typical fluorous separation methods. Recently, the alcohol-functionalized imidazolium salts depicted in Chart 3 were synthesized and applied, in the presence of PdCl 2 , in the Heck reaction of aryl bromides with acrylates under mild and aerobic conditions.…”

Section: Methodsmentioning

confidence: 99%

Recent Developments in the Applications of Palladium Complexes Bearing N-Heterocyclic Carbene Ligands

Poyatos¹

2011

COC

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“…40 Moreover, the preparation of a bis[(tridecafluorooctyl)imidazol-2-ylidene]palladium complex with a pyridine ligand, 41 and its use in the MizorokiHeck reaction of 4-iodotoluene and 1-octene have been described. 42 New polymeric materials containing imidazolium moieties have been synthesized via a modification of commercially available Merrifield resin, 43 or polyisobutylene (PIB) oligomers 44 by reaction with imidazole derivatives. These functionalized polymers have been employed in the preparation of NHCpalladium-supported materials, which effectively catalyzed the MizorokiHeck reaction.…”

Section: ç Mizoroki-heck Reactionmentioning

confidence: 99%

Heterocyclic Carbene–Metal-catalyzed Csp2–Csp2 and Csp–Csp2 Couplings Using Nonmetallic Substrates

Yus¹,

Pastor²

2013

Chemistry Letters

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The use of carbene ligands for transition-metal complexes has been developed in the last decades, being of special interest those carbenes derived from a nitrogen-containing heterocyclic system. An interesting variety of carbenemetal complexes has been tested in the MizorokiHeck reaction. In comparison, few examples can be found for the MatsudaHeck version of this coupling reaction. Additionally, the Sonogashira coupling has been also catalyzed with different carbenemetal catalysts. Ç IntroductionN-Heterocyclic carbenes (NHCs) have emerged in the last years as a new family of ligands with interesting electronic and structural properties.1 The combination of their strong ·-donor and poor ³-acceptor abilities results in good coordination stability and versatility. Consequently, the use of NHC ligands based on imidazolium ions and related heterocycles has appeared as an alternative to phosphanes in the design of new organometallic catalysts.2 One of the main advantages of employing NHC-based catalysts compared with phosphanebased ones is that they are far less prone to oxidation, allowing their prolonged use, and reuse. Although NHCs were presented as simple tertiary phophane mimics, they have been recognized as much more over the past decade. Therefore, NHC ligands have become an interesting alternative to other types of ligands in different cross-coupling catalytic reactions mediated by transition metals.3 Moreover, the easy introduction of chiral elements in the corresponding precursors have made chiral NHCs promising chiral ligands in metal-based asymmetric catalysis. 4 The comparison between phosphane and NHC ligands, from a mechanistic point of view, has been studied, clear differences being found.5 First, the possibility of carbene ligand dissociation is greatly reduced due to its stronger donor ability; and second, the reactivity of the NHCmetal complex is higher probably caused by the lack of back-donation from the metal to the carbene ligand. Jutand and co-workers studied the reactivity of monocarbene and bis(carbene) Pd(0) complexes toward the oxidative addition of aryl halides, concluding that the electronic and steric properties of the carbene ligand are important factors in this step of the catalytic process. 6 Among the carboncarbon coupling reactions, the activation of a CH from an alkene (MizorokiHeck reaction) or an alkyne (Sonogashira reaction) are of special interest. This highlight review describes the progress on the topic of NHC ligands for transition-metal-catalyzed coupling reactions, employing nonmetallic reagents. Thus, both different NHC precursors and NHCmetal complexes with catalytic activity in the Mizoroki Heck, MatsudaHeck, and Sonogashira reactions are compiled. Ç Mizoroki-Heck ReactionIn 1995, Herrmann and co-workers introduced the use of bis(NHC)Pd complexes as catalysts with long-term stability in the MizorokiHeck reaction.7 Indeed, the carbenes derived from imidazole stabilized the palladium complexes due to their pronounced donor properties, being more stable toward...

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Synthesis of bis(polyfluoroalkylated)imidazolium salts as key intermediates for fluorous NHC ligands

Cited by 43 publications

References 33 publications

Synthesis and Sorption Analysis of Task-specific Fluorous Ionic Liquids

Synthesis and Sorption Analysis of Task-specific Fluorous Ionic Liquids

Recent Developments in the Applications of Palladium Complexes Bearing N-Heterocyclic Carbene Ligands

Heterocyclic Carbene–Metal-catalyzed Csp2–Csp2 and Csp–Csp2 Couplings Using Nonmetallic Substrates

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