Introductory Guide to Organonickel Chemistry

Tamaru, Yoshinao

doi:10.1002/3527604847.ch1

Cited by 60 publications

(81 citation statements)

References 24 publications

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“…1,2 Nickel was isolated in 1751 and named after the “devil Nick ore,” a copper-nickel ore resistant to copper extraction. In the 1890s, Ludwig Mond observed one of the unusual reactivity patterns of nickel: elemental nickel and CO reacted at room temperature to form Ni(CO) 4 , an extremely toxic, low-boiling liquid, which could be used to purify the metal.…”

Section: Introductionmentioning

confidence: 99%

“…Many excellent books and reviews of organonickel chemistry in general, 2 as well as of specific transformations (e.g., reductive coupling 3 and cross-coupling 4 ), already exist. Consequently, we have chosen to focus on key advances in nickel-catalyzed reactions since 2005 and to highlight how researchers can take advantage of nickel’s characteristic properties and reactivity to perform innovative and useful transformations.…”

Section: Introductionmentioning

confidence: 99%

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Recent advances in homogeneous nickel catalysis

Tasker

Standley

Jamison

2014

Nature

1,938

1,098

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Preface The field of nickel catalysis has made tremendous advances in the past decade. There are several key properties of nickel that have allowed for a broad range of innovative reaction development, such as facile oxidative addition and ready access to multiple oxidation states. In recent years, these properties have been increasingly understood and leveraged to perform transformations long considered exceptionally challenging. Herein, we discuss some of the most recent and significant developments in homogeneous nickel catalysis with an emphasis on both synthetic outcome and mechanism.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Recent advances in homogeneous nickel catalysis

Tasker

Standley

Jamison

2014

Nature

1,938

1,098

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show abstract

“…Historically, a number of organometallic nickel complexes are highly active alkyne trimerization catalysts. 23d,29 Electronically, Ni(IPr) 2 and Ni(SIPr) 2 would also fit this motif. Strong σ-donation to a coordinatively unsaturated Ni 0 would allow for facile oxidative homocoupling and subsequent insertion.…”

Section: Evidence For a Heterocoupling Pathwaymentioning

confidence: 87%

Mechanistic Evaluation of the Ni(IPr)₂-Catalyzed Cycloaddition of Alkynes and Nitriles To Afford Pyridines: Evidence for the Formation of a Key η¹-Ni(IPr)₂(RCN) Intermediate

2013

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A detailed mechanistic evaluation of the Ni(IPr)2-catalyzed [2+2+2]-cycloaddition of diynes and nitriles was 2 conducted. Through kinetic analysis of these reactions, observed regioselectivities of the products, and stoichiometric reactions, Ni(IPr)2-catalyzed cycloadditions of diynes and nitriles appear to proceed by a heterooxidative coupling mechanism, contrary to other common cycloaddition catalysts. Reaction profiles demonstrated strong dependence in nitrile, resulting in variable nitrile-dependent resting states. Strong coordination and considerable steric bulk of the carbene ligands facilitate selective initial binding of nitrile thereby forcing a heterocoupling pathway. In situ IR data suggests the initial binding of the nitrile resides in a rare, η1-bound conformation. Following nitrile coordination are a rate-determining hapticity shift of the nitrile and subsequent loss of carbene. Alkyne coordination then leads to heterooxidative coupling, insertion of the pendant alkyne, and reductive elimination to afford pyridine products.

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“…1 In the late 1990s, new strategies for nickel-catalyzed coupling of two π-components to produce a new σ-bond between them and a new σ-bond with an organometallic reducing agent were being developed, a field later known as reductive coupling. 2 Although intramolecular reductive cyclizations were well precedented, the first intermolecular reductive three-component coupling was published by Montgomery and coworkers in 1997, and involved reaction of alkynes and aldehydes to give allylic alcohols ( 3 , Scheme 1a).…”

Section: Reductive Coupling Reactions Of Alkynesmentioning

confidence: 99%

Nickel Catalysis: Synergy between Method Development and Total Synthesis

et al. 2015

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Natural products are a continual source of inspiration for chemists, particularly for organic chemists engaged in reaction development and methodology. In the early stages of our research program, we were drawn to macrocyclic natural products containing allylic alcohol moieties, such as (−)-terpestacin (1, Figure 1). We envisioned, in an ideal case, an intramolecular reductive coupling (a field still in its infancy at the time) could be developed to join an alkyne and an aldehyde to yield this allylic alcohol, simultaneously closing the macrocycle. For this reason we began studying reductive coupling as a tool for C–C bond formation. Additionally, as our program developed, it became clear that a number of other natural products, such as amphidinolide T1 (2), which, although they do not contain allylic alcohols, could be produced in an analogous fashion after modification of the allylic alcohol formed from such a macrocyclization.

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Introductory Guide to Organonickel Chemistry

Cited by 60 publications

References 24 publications

Recent advances in homogeneous nickel catalysis

Recent advances in homogeneous nickel catalysis

Mechanistic Evaluation of the Ni(IPr)₂-Catalyzed Cycloaddition of Alkynes and Nitriles To Afford Pyridines: Evidence for the Formation of a Key η¹-Ni(IPr)₂(RCN) Intermediate

Nickel Catalysis: Synergy between Method Development and Total Synthesis

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Introductory Guide to Organonickel Chemistry

Cited by 60 publications

References 24 publications

Recent advances in homogeneous nickel catalysis

Recent advances in homogeneous nickel catalysis

Mechanistic Evaluation of the Ni(IPr)2-Catalyzed Cycloaddition of Alkynes and Nitriles To Afford Pyridines: Evidence for the Formation of a Key η1-Ni(IPr)2(RCN) Intermediate

Nickel Catalysis: Synergy between Method Development and Total Synthesis

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Mechanistic Evaluation of the Ni(IPr)₂-Catalyzed Cycloaddition of Alkynes and Nitriles To Afford Pyridines: Evidence for the Formation of a Key η¹-Ni(IPr)₂(RCN) Intermediate