The Negishi Catalysis: Full Study of the Complications in the Transmetalation Step and Consequences for the Coupling Products

Pozo, Juan del; Salas, Gorka; Álvarez, Rosana; Casares, Juan A.; Espinet, Pablo

doi:10.1021/acs.organomet.6b00660

Cited by 44 publications

(34 citation statements)

References 51 publications

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“…1]. The catalytic processes can suffer complications due to the reversibility of these transmetalations and the existence of undesired secondary transmetalations …”

Section: Figurementioning

confidence: 99%

Rh^IAr/Au^IAr′ Transmetalation: A Case of Group Exchange Pivoting on the Formation of M−M′ Bonds through Oxidative Insertion

et al. 2019

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By combining kinetic experiments, theoretical calculations, and microkinetic modeling, we show that Pf/Rf (C6F5/C6Cl2F3) exchange between [AuPf(AsPh3)] and trans‐[RhRf(CO)(AsPh3)2] does not occur by typical concerted Pf/Rf transmetalation via electron‐deficient double bridges. Instead, it involves asymmetric oxidative insertion of the RhI complex into the (Ph3As)Au−Pf bond to produce a [(Ph3As)Au−RhPfRf(CO)(AsPh3)2] intermediate, followed by isomerization and reductive elimination of [AuRf(AsPh3)]. Interesting differences were found between the LAu−Ar asymmetric oxidative insertion and the classical oxidative addition process of H2 to Vaska complexes.

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“…1]. The catalytic processes can suffer complications due to the reversibility of these transmetalations and the existence of undesired secondary transmetalations …”

Section: Figurementioning

confidence: 99%

Rh^IAr/Au^IAr′ Transmetalation: A Case of Group Exchange Pivoting on the Formation of M−M′ Bonds through Oxidative Insertion

et al. 2019

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“…Wang and co-workers on the nickel-catalyzed Kumada-Tamao-Corriu (KTC) reaction showed that off-cycle species can originate from an unusual retro-transmetallation step, 149 which had also been observed with palladium complexes. 150,151,152 The KTC coupling was used to transform 14.4 kcal mol -1 (Ph-OTf). Catalytic experiments confirmed the tolerance to these leaving and functional groups, which yielded a wide variety of products with high yields between 70-94%.…”

Section: Off-cycle Approach To Nickel Catalystsmentioning

confidence: 99%

Designing Pd and Ni Catalysts for Cross-Coupling Reactions by Minimizing Off-Cycle Species

Balcells

Nova

2018

ACS Catal.

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This perspective presents an overview on recent experimental and computational studies on the off-cycle reactions of palladium-and nickel-catalyzed cross-couplings. Several reactions entering or leaving the catalytic cycle have been characterized, including the activation of Pd(II) precatalysts by H-shift and the deactivation of Ni(II) precatalysts by comproportionation. A fundamental difference between the off-cycle chemistries of palladium and nickel is the larger diversity of species yielded by the latter, with a rich combination of different oxidation states, nuclearity and ligand coordination modes. The molecular-level understanding of off-cycle reactions has enabled new catalyst design strategies, including the stereoelectronic fine-tuning of the ligands aimed at maximizing the activation of the precatalyst meanwhile preventing its deactivation. Despite several challenges, which concern both experiments (e.g. isolation and characterization of transient species) and computations (e.g. comprehensive mapping of the potential energy surface), this approach has already been applied with success in the optimization of popular catalytic platforms (e.g. NHC-Pd-allyl precatalysts) and shows promise for the development of highly active and robust catalysts based on nickel.

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“…Numerous research groups have used the NHC-Pd metal catalysts in the formation of a C-C bond. Recently, the Pdbased NHC complexes have been applied in organic chemistry for important C-C bond formations such as the Suzuki, 34 Heck, 34 Negishi, 35 Stille, 36 Hiyama coupling, 37 Sonogashira coupling, 38 Kumada coupling 39 and Buchwald-Hartwig amination 40 reactions.…”

Section: Introductionmentioning

confidence: 99%

Novel 2-hydroxyethyl substituted N-coordinate-Pd(II)(NHC) and bis(NHC)Pd(II) complexes: Synthesis, characterization and the catalytic activity in the direct arylation reaction

2019

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The direct arylation reaction has attracted attention in recent years especially because of its environment-friendly properties. In this study, we researched the synthesis of 2-hydroxyethyl substituted bis(NHC)Pd(II) complexes and also the synthesis of N-coordinate-Pd(II)(NHC) complexes containing Nbound benzimidazolium from palladium acetate ([Pd(CH 3 COO) 2 ]) with 1,3-disubstituted benzimidazolium halides in DMSO. All the complexes have been characterized by using 1 H NMR, 13 C NMR, FTIR spectroscopy and elemental analysis techniques. The molecular and crystal structure of one of the complexes is confirmed by using single-crystal X-ray diffraction. These complexes have been examined as the catalyst in the direct arylation reaction with 2-n-butylfuran and 2-n-butylthiophene and have demonstrated excellent activity in this reaction.

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The Negishi Catalysis: Full Study of the Complications in the Transmetalation Step and Consequences for the Coupling Products

Cited by 44 publications

References 51 publications

Rh^IAr/Au^IAr′ Transmetalation: A Case of Group Exchange Pivoting on the Formation of M−M′ Bonds through Oxidative Insertion

Rh^IAr/Au^IAr′ Transmetalation: A Case of Group Exchange Pivoting on the Formation of M−M′ Bonds through Oxidative Insertion

Designing Pd and Ni Catalysts for Cross-Coupling Reactions by Minimizing Off-Cycle Species

Novel 2-hydroxyethyl substituted N-coordinate-Pd(II)(NHC) and bis(NHC)Pd(II) complexes: Synthesis, characterization and the catalytic activity in the direct arylation reaction

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The Negishi Catalysis: Full Study of the Complications in the Transmetalation Step and Consequences for the Coupling Products

Cited by 44 publications

References 51 publications

RhIAr/AuIAr′ Transmetalation: A Case of Group Exchange Pivoting on the Formation of M−M′ Bonds through Oxidative Insertion

RhIAr/AuIAr′ Transmetalation: A Case of Group Exchange Pivoting on the Formation of M−M′ Bonds through Oxidative Insertion

Designing Pd and Ni Catalysts for Cross-Coupling Reactions by Minimizing Off-Cycle Species

Novel 2-hydroxyethyl substituted N-coordinate-Pd(II)(NHC) and bis(NHC)Pd(II) complexes: Synthesis, characterization and the catalytic activity in the direct arylation reaction

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Rh^IAr/Au^IAr′ Transmetalation: A Case of Group Exchange Pivoting on the Formation of M−M′ Bonds through Oxidative Insertion

Rh^IAr/Au^IAr′ Transmetalation: A Case of Group Exchange Pivoting on the Formation of M−M′ Bonds through Oxidative Insertion