A novel hydrophobic fluorous ionic liquid for ligand-free Mizoroki–Heck reaction

Gaikwad, D. S.; Park, YoonKook; Pore, Dattaprasad M.

doi:10.1016/j.tetlet.2012.04.027

Cited by 32 publications

(7 citation statements)

References 31 publications

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“…As one of the organic transformations honored with the Nobel Prize, − the Mizoroki–Heck reaction − has been and still is being intensely studied experimentally and theoretically. − The development of this powerful palladium-catalyzed C–C bond-forming process enabled the facile synthesis of stilbenes from styrene derivatives and aryl halides as target molecules for medicinal − and materials − chemistry on a laboratory − and industrial − scale. A multitude of catalyst systems has been established for the Mizoroki–Heck reaction, , among them not only phosphines − and N-heterocyclic carbenes (NHCs) − as ligands but also preformed palladium nanoparticles − and “ligand-free” systems − in ionic liquids. − While aryl bromides are typically the coupling partner, many developed systems are also able to couple the less reactive aryl chlorides. − …”

Section: Introductionmentioning

confidence: 99%

Understanding Anionic “Ligandless” Palladium Species in the Mizoroki–Heck Reaction

Schroeter

Straßner

2018

Inorg. Chem.

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The anionic complex [NBu][Pd(DMSO)Cl], as a "ligandless" system, was shown to be an active catalyst in the Mizoroki-Heck coupling of aryl chlorides in the absence of strongly σ-donating ligands. To investigate the experimentally observed influence of halides and the amount of water on the catalytic activity, we employed a combination of experiments and theoretical calculations. The presence of water was shown to be critical for the formation of the active palladium(0) species by oxidation of in situ generated tributylamine. Oxidative addition to an anionic palladium(0) species was found to be the rate-determining step of the catalytic cycle. For the ensuing steps, both neutral and anionic pathways were considered. It was shown that, in the absence of strongly σ-donating neutral ligands, chloride ions stabilize the catalytic intermediates. Therefore, an anionic pathway is preferred, which explains the need for tetrabutylammonium chloride as an additive. The study of the influence of bromide ions on the catalytic activity revealed that the strongly exergonic displacement of the neutral substrates by bromide ions lowers the catalytic activity.

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Section: Introductionmentioning

confidence: 99%

Understanding Anionic “Ligandless” Palladium Species in the Mizoroki–Heck Reaction

Schroeter

Straßner

2018

Inorg. Chem.

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“…Consequently, the 2010 Nobel Prize in chemistry was awarded jointly to Richard F. Heck, Ei-ichi Negishi, and Akira Suzuki . Particularly interesting, in terms of cost and atom efficiency, is the concept of “ligandless” catalytic systems, e.g., the absence of stabilizing phosphine or N -heterocyclic carbene (NHC) ligands, or the use of nanoparticles in ionic liquids …”

Section: Introductionmentioning

confidence: 99%

Cross-Coupling Catalysis by an Anionic Palladium Complex

2017

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Recent studies have shown that anionic palladium complexes are viable catalysts for a range of catalytic cross-coupling reactions. We present a one-step synthesis of the anionic "ligandless" palladium complex [NBu 4 ][Pd-(DMSO)Cl 3 ] together with its crystal structure. This compound has been shown to be an active precatalyst in the Mizoroki−Heck reaction. Under Jeffery conditions, activated aryl chlorides can be coupled in yields of up to 94% without the need of an additional ligand. The presence of a small amount of water was necessary for product formation. An Amatore−Jutand-type catalytic cycle is consistent with the results presented herein. For comparison with the known mixed complex [(pym-Im-Me) 2 PdCl][Pd(DMSO)Cl 3 ], the cationic complex [(pym-Im-Me) 2 PdCl]PF 6 (pym = pyrimidyl, Im = imidazolin-2-ylidene) has been synthesized and characterized using standard techniques.

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“…[31][32][33][34][35][36] Richard F. Heck was, together with Eiichi Negishi and Akira Suzuki, awarded with the 2010 Nobel prize in chemistry for their work on transition metal catalyzed cross-coupling reactions. [37,38] As solvents for the Mizoroki-Heck reaction, a variety of ionic liquids e. g. ammonium, [39][40][41][42] imidazolium, [43][44][45][46][47] pyridinium, [48] and phosphonium [49] based ILs have been used. In this work, we describe the use of tunable aryl alkyl ionic liquids (TAAILs) as solvents in the Mizoroki-Heck reaction.…”

Section: Introductionmentioning

confidence: 99%

The Mizoroki‐Heck Reaction in Tunable Aryl Alkyl Ionic Liquids

2022

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We report the use of imidazolium based tunable aryl alkyl ionic liquids (TAAILs) as solvents in the Mizoroki-Heck reaction. Different commercially available palladium sources, inorganic bases, TAAILs and reaction conditions were tested for the synthesis of trans-stilbene using bromobenzene and styrene. A variety of different stilbene derivatives were synthesized with exclusive formation of the (E)-isomers and isolated yields up to 97 %. We were able to optimize the reaction conditions using only 0.25 mol% of Pd(OAc) 2 as the catalyst and a reaction time of 4 hours. No additional ligands or additives are used in the reaction. The catalytic system using TAAILs achieved higher yields than commercially available imidazolium and phosphonium ionic liquids, demonstrating the potential of tailored ionic liquids as a reaction medium for the Mizoroki-Heck reaction.

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A novel hydrophobic fluorous ionic liquid for ligand-free Mizoroki–Heck reaction

Cited by 32 publications

References 31 publications

Understanding Anionic “Ligandless” Palladium Species in the Mizoroki–Heck Reaction

Understanding Anionic “Ligandless” Palladium Species in the Mizoroki–Heck Reaction

Cross-Coupling Catalysis by an Anionic Palladium Complex

The Mizoroki‐Heck Reaction in Tunable Aryl Alkyl Ionic Liquids

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