Mechanisms of Nickel-Catalyzed Cross-Coupling Reactions

Diccianni, Justin B.; Diao, Tianning

doi:10.1016/j.trechm.2019.08.004

Cited by 440 publications

(371 citation statements)

References 117 publications

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“…(2) We demonstrate the following order of reactivity of NHC ligands in amide bond cross-coupling: IPr > IMes > IPaul ≈ IPr*. (3) We further establish that both the neutral and the cationic complexes are efficient catalysts for the Suzuki-Miyaura cross-coupling of amides. (4) Kinetic studies demonstrate that the reactions reach full conversion in < 1 h at 80 °C.…”

Section: Introductionmentioning

confidence: 70%

“…Furthermore, we have established the order of reactivity of NHC ligands in [CpNi(NHC)Cl] complexes as IPr > IMes > IPaul ≈ IPr*, and showed that both neutral and cationic complexes serve as efficient catalysts for amide bond cross-coupling. Reaction profile studies demonstrated that these reactions are complete in < 1 h at 80 • C. In a broader context, the present method should be evaluated in comparison with other known approaches to biaryl ketones from amides [3][4][5][6][7][8][9][10] and acyl electrophiles [15]. The use of Ni catalysis [1-3] and the beneficial performance of Ni-NHC complexes [25][26][27][28][29] may accelerate the development of new approaches to activating amide bonds.…”

Section: Discussionmentioning

confidence: 99%

“…Nickel catalysis has recently garnered significant attention, enabling cleavage of unreactive bonds by this abundant 3D transition metal [1][2][3]. Simultaneously, major advances have been made in amide cross-coupling, wherein highly selective oxidative addition of the N-C(O) bond enables to exploit the traditionally unreactive amides as a novel class of acyl and aryl electrophiles [4][5][6][7][8][9][10].…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Suzuki–Miyaura Cross-Coupling of Amides Using Well-Defined, Air- and Moisture-Stable Nickel/NHC (NHC = N-Heterocyclic Carbene) Complexes

2020

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In this Special Issue on N-Heterocyclic Carbenes and Their Complexes in Catalysis, we report the first example of Suzuki–Miyaura cross-coupling of amides catalyzed by well-defined, air- and moisture-stable nickel/NHC (NHC = N-heterocyclic carbene) complexes. The selective amide bond N–C(O) activation is achieved by half-sandwich, cyclopentadienyl [CpNi(NHC)Cl] complexes. The following order of reactivity of NHC ligands has been found: IPr > IMes > IPaul ≈ IPr*. Both the neutral and the cationic complexes are efficient catalysts for the Suzuki–Miyaura cross-coupling of amides. Kinetic studies demonstrate that the reactions are complete in < 1 h at 80 °C. Complete selectivity for the cleavage of exocyclic N-acyl bond has been observed under the experimental conditions. Given the utility of nickel catalysis in activating unreactive bonds, we believe that well-defined and bench-stable [CpNi(NHC)Cl] complexes will find broad application in amide bond and related cross-couplings of bench-stable acyl-electrophiles.

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Section: Introductionmentioning

confidence: 70%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Suzuki–Miyaura Cross-Coupling of Amides Using Well-Defined, Air- and Moisture-Stable Nickel/NHC (NHC = N-Heterocyclic Carbene) Complexes

2020

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“…Notably, in this case a C(sp 3 )–C(sp 3 ) bond formation was realized, despite the low propensity of alkyl‐alkyl groups to give reductive elimination in the case of Ni complexes, and the possible occurrence of parasite processes (e.g. β‐H elimination) ,. [44b]…”

Section: Catalytic Cycle Being Closed By a Co‐catalystmentioning

confidence: 98%

“…This last feature expands the scope of cross‐coupling reactions to metal‐alkyl intermediates, that would otherwise decompose, e.g. with Pd‐based catalysts . Recently, these peculiar properties have been exploited in the field of photocatalysis as well, significantly extending the benefits of light‐triggered organic synthesis to new reaction partners, notably alkyl/aryl halides …”

Section: Catalytic Cycle Being Closed By a Co‐catalystmentioning

confidence: 99%

The Dark Side of Photocatalysis: One Thousand Ways to Close the Cycle

Capaldo

Ravelli

2020

Eur J Org Chem

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Photocatalytic strategies have recently revolutionized the field of organic synthesis. However, while the progress has been impressive in terms of reported methodologies, less attention has been devoted to mechanistic aspects. In this regard, key to the development of efficient strategies is the recovery of the exhausted photocatalyst formed upon quenching of the excited state. This review summarizes the different ways available to turn over the photocatalyst and classifies them according to the species responsible for this step, being a reaction intermediate, a co‐catalyst, a reaction partner or an electrode. Finally, an analysis of the common aspects of the described alternatives is offered, also showcasing how the tuning of the photocatalyst turn‐over step can completely divert the reaction outcome.

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Synthesis, Properties, and Reactivity of Linear Open‐Shell 3d‐Metal(I) Complexes

Werncke

Gómez

2022

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Linear complexes with two‐coordinate, open‐shell 3d‐metal(I) ions are a young and rare class of compounds in coordination chemistry and are known so far for chromium to nickel. These complexes combine an uncommon coordination motif with an, for these metals, unusual oxidation state. The isolation of such compounds relies mostly on the use of sterically encumbering and/or electronically stabilizing ligands, such as bulky amides or N ‐heterocyclic carbenes, to support the highly unsaturated metal center. Given the labile nature of these linear complexes as well as their only recent history, the physical properties, as well as their reactivity concerning small molecules and various bonding types are only partially explored. Reports concerning their respective behavior indicate a high potential, for example remarkable single‐molecule magnetic properties or first use in catalysis. Herein, we wish to give a comprehensive overview about the current knowledge, and by this shed the scientific spotlight on this, in our eyes, underused yet highly intriguing class in coordination chemistry.

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Mechanisms of Nickel-Catalyzed Cross-Coupling Reactions

Cited by 440 publications

References 117 publications

Suzuki–Miyaura Cross-Coupling of Amides Using Well-Defined, Air- and Moisture-Stable Nickel/NHC (NHC = N-Heterocyclic Carbene) Complexes

Suzuki–Miyaura Cross-Coupling of Amides Using Well-Defined, Air- and Moisture-Stable Nickel/NHC (NHC = N-Heterocyclic Carbene) Complexes

The Dark Side of Photocatalysis: One Thousand Ways to Close the Cycle

Synthesis, Properties, and Reactivity of Linear Open‐Shell 3d‐Metal(I) Complexes

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