The Synthesis of Some Perhydrobenzimidazolinium Salts and Their Application in Pd-Carbene Catalyzed Heck and Suzuki Reactions

Yiğit, Murat

doi:10.3390/molecules14062032

Cited by 19 publications

(12 citation statements)

References 42 publications

(42 reference statements)

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“…It can be show these salts are an effective ligand precursor for the coupling of unactivated, activated and deactivated aryl bromides with styrene. These results are in agreement with other reports 34,38. In summary, eight 1,3-dialkylperhydrobenzimidazolinium chloride salts 3a-h were prepared by reacting N,N'-dialkylcyclohexanediamine, triethyl orthoformate and ammonium chloride, and their catalytic activities in the Heck coupling reactions were investigated.…”

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confidence: 91%

“…[34][35][36][37] We recently reported the synthesis of N-heterocyclic carbene derivative ligands and their palladium(II) carbene complexes and investigated for catalytic activity in Heck and Suzuki reactions. [38][39][40][41][42][43] In this article we wish to report the synthesis of new 1,3-dialkylperhydrobenzimidazolinium chloride salts 3a-h (scheme 1), and their application to Heck cross-coupling with aryl halides.…”

Section: Good Catalysts For the Heck Reactions Of Unactivated Aryl Chmentioning

confidence: 99%

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Synthesis of 1,3-Dialkylperhydrobenzimidazolinium Salts and Their Catalytic Properties in Heck Reactions

Yiğit¹,

Bayam²,

Yığıt³

et al. 2013

HETEROCYCLES

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Novel eight 1,3-dialkylperhydrobenzimidazolinium chloride salts 3a-h were prepared as precursors of N-heterocyclic carbenes by reacting N,N'-dialkylcyclohexanediamine, triethyl orthoformate and ammonium chloride. The salts were characterized spectroscopically and the complexes formed in situ from Pd(OAc) 2 and 3 have been tested as catalysts in homogenous Heck coupling reactions.The Palladium-catalyzed Mizoroki-Heck cross-coupling reaction of an olefin with aryl halides under basic conditions is one of the highly efficient tools for the carbon-carbon bond formation in organic synthesis. 1-3 Phosphines generally have been used as ligands for the palladium-catalyzed Heck and Suzuki coupling reactions. However, the phosphine ligands are expensive, toxic and sensitive to air and the moisture. 4-7 The strong electron donating property of N-heterocyclic carbene ligands leads to metal complexes with high stability against heat, air and moisture. These properties of N-heterocyclic carbene ligands make them alternatives to tertiary phosphines used in different transition metal-catalyzed reactions such as C-C and C-N arylation, olefin metathesis, hydrogenation, hydrosilylation and CO-ethylene co-polymerization reactions. 8-19 Apart from phosphine and N-heterocyclic carbene ligands,

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confidence: 91%

Section: Good Catalysts For the Heck Reactions Of Unactivated Aryl Chmentioning

confidence: 99%

Synthesis of 1,3-Dialkylperhydrobenzimidazolinium Salts and Their Catalytic Properties in Heck Reactions

Yiğit¹,

Bayam²,

Yığıt³

et al. 2013

HETEROCYCLES

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“…This method is very useful because the free carbene ligand, which is often hard to handle, does not need to be isolated. Our previously reported [37,38] symmetrical 1,3-dialkylperhydrobenzimidazolium salts were synthesized in high yields from the N,N 0 -dialkylcyclohexan-1,2-diamines, triethyl orthoformate and ammonium chloride. The silver(I) NHC complexes 2a-c were prepared by reaction of the 1,3-dialkylperhydrobenzimidazolium salts as NHC ligand precursors with Ag 2 O in dichloromethane at room temperature in the dark (Scheme 1).…”

Section: Synthesis Of the Complexesmentioning

confidence: 99%

Synthesis of silver(I) and palladium(II) N-heterocyclic carbene complexes and their use as catalysts for the direct C5 arylation of heteroaromatic compounds

et al. 2016

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Silver(I) N-heterocyclic carbene complexes were synthesized in good yields by the reactions of 1,3-dialkylperhydrobenzimidazolium salts with silver(I) oxide in dichloromethane. The silver complexes were used as carbene-transfer agents to synthesize palladium(II) N-heterocyclic carbene complexes. All of the complexes were characterized by physicochemical and spectroscopic methods. The new palladium complexes were tested as catalysts in the direct C5 arylation of 2-n-butylfuran, 2-nbutylthiophene and 2-n-propylthiazole with aryl bromides at 130°C in N,N-dimethylacetamide. The arylation reactions proceeded selectively at the C5 position of the heteroaromatic compounds, and the corresponding coupling products were obtained in moderate to good yields by using 0.5 mol% of the palladium complex.

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“…18 Additionally, 1,3-dialkylperhydrobenzimidazolium salts have been employed in combination with palladium(II) acetate (in 2:1 ratio) to catalyze the coupling of aryl bromides (i.e., bromobenzene, 4-bromotoluene, 4-bromoanisole, and 4-bromobenzaldehyde) with styrene, giving the corresponding stilbenes in good yields (81 98%). 19 Moreover, quaternization of caffeine with methyl iodide formed the corresponding 1,3,7,9-tetramethylxanthinium salt, which has been employed in the preparation of the bis(NHC) palladium complex 28 (Chart 2). 20 Complex 28-catalyzed satisfactorily the reaction of iodobenzene and 4-bromoacetophenone with methyl acrylate in water.…”

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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The Synthesis of Some Perhydrobenzimidazolinium Salts and Their Application in Pd-Carbene Catalyzed Heck and Suzuki Reactions

Cited by 19 publications

References 42 publications

Synthesis of 1,3-Dialkylperhydrobenzimidazolinium Salts and Their Catalytic Properties in Heck Reactions

Synthesis of 1,3-Dialkylperhydrobenzimidazolinium Salts and Their Catalytic Properties in Heck Reactions

Synthesis of silver(I) and palladium(II) N-heterocyclic carbene complexes and their use as catalysts for the direct C5 arylation of heteroaromatic compounds

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

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