Efficient Iron‐Catalyzed Kumada Cross‐Coupling Reactions Utilizing Flow Technology under Low Catalyst Loadings

@article{Buono2016EfficientIK,
  title={Efficient Iron‐Catalyzed Kumada Cross‐Coupling Reactions Utilizing Flow Technology under Low Catalyst Loadings},
  author={Frederic G Buono and Yongda Zhang and Zhulin Tan and Andrew T. Brusoe and Bing-Shiou Yang and Jon C. Lorenz and Riccardo Giovannini and Jinhua J. Song and Nathan Yee and Chris Hugh Senanayake},
  journal={European Journal of Organic Chemistry},
  year={2016},
  volume={2016},
  pages={2599-2602}
}
An efficient continuous flow iron-catalyzed Kumada cross-coupling was developed for the coupling of 2-chloropyrazine and various aryl Grignard reagents in presence of low catalyst loadings (0.5 mol-%). Compared to batch mode, the continuous flow approach overcomes the exothermicity which enabled longer catalyst lifetime, facilitated scale-up and significantly improved the yield. To the best of our knowledge, this is the first example of flow iron-catalyzed Kumada cross-coupling reactions which… 
View via Publisher
15 Citations
Highly Influential Citations
1
Background Citations
1

15 Citations

Application of a Preformed Pd-BIDIME Precatalyst to Suzuki-Miyaura Cross-Coupling Reaction in Flow.

TLDR
Using flow technology, high yield and reproducible Suzuki cross-coupling reaction for one of the authors' key intermediates was achieved with Pd loadings as low as 0.5 mol % and responds to the challenge of improving process greenness.

Transition-Metal-Catalyzed Cross-Coupling Reactions of Grignard Reagents

Transition-metal-catalyzed cross-coupling of organo­halides, ethers, sulfides, amines, and alcohols (and derivatives thereof) with Grignard reagents, known as the Kumada–Tamao–Corriu reaction, can be…

Inherent vs Apparent Chemoselectivity in the Kumada-Corriu Cross-Coupling Reaction.

TLDR
It is demonstrated that high-yielding couplings can occur in the presence of many electrophilic and heterocyclic functional groups, and the mechanistic reason for the effectiveness of this strategy is uncovered by continuous-infusion ESI-MS studies.

Iron-Catalyzed Cross-Couplings in the Synthesis of Pharmaceuticals: In Pursuit of Sustainability.

TLDR
The strategic benefits of using iron catalysts as green and sustainable alternatives to precious metals in cross-coupling applications for the synthesis of pharmaceuticals are critically discussed.

Homogeneous Catalyzed Aryl–Aryl Cross-Couplings in Flow

TLDR
Aryl–aryl cross-coupling reactions are important reactions for the production of various biaryl compounds, focusing on the metal species of the aryl nucleophiles used in the cross-Coupled reactions.

Advances in Kumada–Tamao–Corriu cross-coupling reaction: an update

The formation of the C–C bond is a major and important reaction in synthetic organic chemistry and frequently catalyzed by transition-metal catalysts. Among them, Kumada–Tamao–Corriu coupling…

Cross-Coupling Reaction of Aryl Halides with Grignard Reagents Catalyzed by Nickel Complexes Supported 2-pyrazolinyl-9-aryl-1, 10-phenanthrolines

Four nickel complexes[NiCl2L](1-4) supported by a tridentate pyrazolyl-based phenanthroline ligand (L1-L4) have been developed for C-C coupling reactions. The nickel complexes exhibited moderate…

Copper-catalyzed asymmetric hydrogenation of 2-substituted ketones via dynamic kinetic resolution† †Electronic supplementary information (ESI) available. CCDC 1816601 and 1816602. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8sc00434j

TLDR
A new class of tunable heterophosphole dimeric ligands have been designed and synthesized and described in a number of publications.

Emerging Trends in Flow Chemistry and Applications to the Pharmaceutical Industry.

TLDR
A combination of simplified and automated systems are discussed, demonstrating how flow chemistry solutions can be tailored to fit the specific needs of a project.

Organometallic Synthesis in Flow

References

SHOWING 1-10 OF 19 REFERENCES

Nickel-catalysed Negishi cross-coupling reactions: scope and mechanisms.

TLDR
This tutorial review presents the more recent advances in Ni-catalysed Negishi cross-couplings for the formation of different kinds of C-C bonds and discusses their proposed reaction mechanisms.

Recent Advances in Iron-Catalyzed Csp2–Csp2 Cross-Couplings

The present review article highlights recent progress in the field of iron-catalyzed cross-coupling reactions between Csp² centers. The reaction scope of various iron-catalyzed couplings between…

Selective Kumada biaryl cross-coupling reaction enabled by an iron(III) alkoxide-N-heterocyclic carbene catalyst system.

TLDR
Amongst the alkoxide and amide counterions investigated, tert-butoxide was the most effective in inhibiting the homocoupling of arylmagnesiums.

First Example of Alkyl–Aryl Negishi Cross-Coupling in Flow: Mild, Efficient and Clean Introduction of Functionalized Alkyl Groups

The first example of an alkyl-aryl Negishi coupling in a practical, sustainable, and high-yielding process using a silica-supported catalyst in flow is described. Excellent conversions and good…

Iron-catalyzed cross-coupling reactions.

TLDR
The method allows for consecutive cross-coupling processes in one pot, as exemplified by the efficient preparation of compound 12, and has been applied to the first synthesis of the cytotoxic marine natural product montipyridine 8.

The promise and challenge of iron-catalyzed cross coupling.

TLDR
The preparative aspects of iron-catalyzed cross coupling are encouraging, but the inclination to classify these processes within the characteristic reaction manifold is premature, as mechanistic studies have evolved at a comparatively slow pace.

Iron-catalyzed cross-coupling of N-heterocyclic chlorides and bromides with arylmagnesium reagents.

A simple, practical iron salt catalyzed procedure allows fast cross-couplings of N-heterocyclic chlorides and bromides with various electron-rich and -poor arylmagnesium reagents. A solvent mixture…

Low pressure Pd-catalyzed carbonylation in an ionic liquid using a multiphase microflow system.

A low pressure microflow system was developed for palladium-catalyzed multiphase carbonylation reactions in an ionic liquid. The microflow system resulted in superior selectivity and higher yields in…

Secondary alkyl halides in transition-metal-catalyzed cross-coupling reactions.

TLDR
This Minireview summarizes selected examples of the use of secondary alkyl halides as electrophiles in cross-coupling reactions, with emphasis on the transition metals employed, the mechanistic pathways involved, and implications in terms of the stereochemical outcome of reactions.

Iron-catalyzed selective biaryl coupling: remarkable suppression of homocoupling by the fluoride anion.

In the presence of iron(III) fluoride and 1,3-bis(2,6-di-i-propylphenyl)imidazolinium chloride, aryl magnesium bromides react with aryl chlorides to give the corresponding cross-coupling products,…