Dinuclear Systems in the Efficient Nickel-Catalyzed Kumada–Tamao–Corriu Cross-Coupling of Aryl Halides

Matsubara, Kouki; Yamamoto, Hiroaki; Miyazaki, Satoshi; Inatomi, Takahiro; Nonaka, Keita; Koga, Yuji; Yamada, Yuji; Veiros, Luı́s F.; Kirchner, Karl

doi:10.1021/acs.organomet.6b00451

Cited by 74 publications

(81 citation statements)

References 82 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[7b] Matsubara and co-workers very recently showed that the latter complex triggers Kumada cross-couplings,a nd it was suggested that aN i I dimer or monomer may be involved in the process. [15] Smaller NHC Ni I monomers have also been shown to trigger CÀCa nd CÀN couplings. [9] Ap ronounced ligand effect was observed by Louie et al for the formation of Ni I or Ni II in reactions with (NHC)Ni 0 .…”

mentioning

confidence: 99%

Divergent Reactivity of a Dinuclear (NHC)Nickel(I) Catalyst versus Nickel(0) Enables Chemoselective Trifluoromethylselenolation

et al. 2017

View full text Add to dashboard Cite

We herein showcase the ability of NHC‐coordinated dinuclear NiI–NiI complexes to override fundamental reactivity limits of mononuclear (NHC)Ni0 catalysts in cross‐couplings. This is demonstrated with the development of a chemoselective trifluoromethylselenolation of aryl iodides catalyzed by a NiI dimer. A novel SeCF3‐bridged NiI dimer was isolated and shown to selectively react with Ar−I bonds. Our computational and experimental reactivity data suggest dinuclear NiI catalysis to be operative. The corresponding Ni0 species, on the other hand, suffers from preferred reaction with the product, ArSeCF3, over productive cross‐coupling and is hence inactive.

show abstract

mentioning

confidence: 99%

Divergent Reactivity of a Dinuclear (NHC)Nickel(I) Catalyst versus Nickel(0) Enables Chemoselective Trifluoromethylselenolation

et al. 2017

View full text Add to dashboard Cite

show abstract

“…[13,20] For related dinuclear Ni I complexes,t here has been very recent evidence that carbon-based bridges may in fact be possible. [21] We calculated the predicted selectivities for an n-propyl-bridged Pd I dimer,w hich indicated ac lear C À Br addition preference.B oth C À Cl and C À OTf are predicted to be significantly disfavored (by DDG°= 5.8 and 2.8 kcal mol À1 ). Alternatively,P d 0 PtBu 3 may be active and our computations suggest preferential CÀBr addition (by DDG°= 4.4 and 8.3 kcal mol À1 for Cl and OTf).…”

mentioning

confidence: 99%

Palladium(I) Dimer Enabled Extremely Rapid and Chemoselective Alkylation of Aryl Bromides over Triflates and Chlorides in Air

et al. 2017

View full text Add to dashboard Cite

Disclosed herein is the first general chemoand site-selective alkylation of CÀBr bonds in the presence of COTf,C ÀCl and other potentially reactive functional groups,u sing the air-, moisture-, and thermally stable dinuclear Pd I catalyst, [Pd(m-I)PtBu 3 ] 2 .T he bromo-selectivity is independent of the substrate and the relative positioning of the competing reaction sites,and as such fully predictable. Primary and secondary alkylc hains were introduced with extremely high speed (< 5min reaction time) at room temperature and under open-flask reaction conditions.

show abstract

“…154 Matsubara and co-workers for the Kumada-Tamao-Corriu cross-coupling reaction. 111 In this case, the bimetallic core is stabilized by either one or two p-tolyl bridging ligands (B and C in Figure 17). DFT calculations showed the ability of the -p-tolyl ligand in B to slip into a  1 terminal position, allowing for the oxidative addition of the electrophile across the Ni-Ni bridge.…”

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.

View full text Add to dashboard Cite

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.

show abstract

Dinuclear Systems in the Efficient Nickel-Catalyzed Kumada–Tamao–Corriu Cross-Coupling of Aryl Halides

Cited by 74 publications

References 82 publications

Divergent Reactivity of a Dinuclear (NHC)Nickel(I) Catalyst versus Nickel(0) Enables Chemoselective Trifluoromethylselenolation

Divergent Reactivity of a Dinuclear (NHC)Nickel(I) Catalyst versus Nickel(0) Enables Chemoselective Trifluoromethylselenolation

Palladium(I) Dimer Enabled Extremely Rapid and Chemoselective Alkylation of Aryl Bromides over Triflates and Chlorides in Air

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

Contact Info

Product

Resources

About