Bis(1,5-cyclooctadiene)nickel(0)

Wender, Paul A.; Smith, Thomas E.; Duong, Hung A.; Louie, Janis; Standley, Eric A.; Tasker, Sarah Z.

doi:10.1002/047084289x.rb118.pub3

Cited by 14 publications

(15 citation statements)

References 445 publications

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“…First row metals also tend to undergo more facile ligand exchange and disproportionation, as well as to have multiple energetically accessible coordination geometries, oxidation states, and spin states, all of which complicate the development and mechanistic study of catalytic processes. In addition, many published transformations employ expensive and/or air-sensitive catalyst precursors, such as Ni(cod) 2 , that are not only impractical for use on a large scale but also often negate the economic advantages offered by base metals. Even if an inexpensive metal precursor can be employed, the low cost of the metal will be offset if high loadings of an expensive ligand are required or if catalyst removal from the process stream is mass- and operation-intensive.…”

Section: Discussionmentioning

confidence: 99%

A Pharmaceutical Industry Perspective on Sustainable Metal Catalysis

2018

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As companies grow ever more mindful of the sustainability aspects of their products and supply chains, an increasing focus on the environmental impact of pharmaceutical manufacture spurs innovation from chemists who support this industry. Metal catalysis has the potential to greatly enhance the sustainability of pharmaceutical products, leading to shorter and more efficient synthetic routes and more direct access to single stereoisomeric products. This perspective article seeks to highlight a number of important considerations for the design of new and improved sustainable metal-catalyzed transformations in order to facilitate rapid adoption by the pharmaceutical industry.

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Section: Discussionmentioning

confidence: 99%

A Pharmaceutical Industry Perspective on Sustainable Metal Catalysis

2018

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“…In principle, the use of water instead of EtOH to cleave 4 , providing immediate access to 7 , would also be interesting. Unfortunately, a reaction starting from model substrate 3a proved this approach does not work and only substrate was identified, which is not surprising, based on the known sensitivity of Ni(cod) 2 …”

Section: Resultsmentioning

confidence: 99%

Directed C–H Functionalization Reactions with a Picolinamide Directing Group: Ni-Catalyzed Cleavage and Byproduct Recycling

et al. 2019

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An efficient strategy for the cleavage of the picolinamide directing group (DG) and recycling of the byproduct generated has been developed. In this protocol, picolinamides were first Boc activated into tertiary N-Boc-N-substituted picolinamides. These were then cleaved via a Ni-catalyzed esterification reaction with EtOH to give valuable N-Boc protected amines. Ni(cod)2 was used as a catalyst without any ligands or base additives. The byproduct, ethyl 2-picolinate can be used to install the picolinamide DG in a direct or indirect manner on amines. The protocol exhibits a broad functional group tolerance and high yields. To demonstrate the utility of this approach, it was applied on many selected examples from the recent C–H functionalization literature featuring 2-picolinamide as a DG.

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“…This is especially true in the early stages of reaction optimization, owing to its high commercial availability and ability to coordinate a wide variety of ligands in situ. Nevertheless, its extreme sensitivity to oxygen, moisture, various solvents, and even moderate heat (Figure 1A) [9][10][11] necessitates handling in an inert atmosphere and long-term storage at low temperature. 12 This, in turn, has hindered broad adoption of catalytic reactions that rely on Ni(COD)2 in many settings, particularly in pharmaceutical process development.…”

Section: Introductionmentioning

confidence: 99%

Structurally Diverse Bench-Stable Nickel(0) Pre-Catalysts: A Practical Toolkit for In Situ Ligation Protocols

Kim

Rubel

et al. 2022

Preprint

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A flurry of recent research has centered on harnessing the power of nickel catalysis in organic synthesis. These efforts have been bolstered by contemporaneous synthesis, characterization, and optimization of well-defined nickel (pre)catalysts with diverse structure and reactivity. In this report, we present the development of ten different bench-stable, 18-electron, formally zero-valent nickel–olefin complexes that are shown to be competent pre-catalysts in various reactions. Our investigation includes preparations of novel, bench stable Ni(COD)(L) complexes, in which L = quinone, cyclopentadienone, thiophene-S-oxide, and fulvene. Characterization by a battery of techniques, including NMR, IR, single-crystal X-ray diffraction, cyclic voltammetry, thermogravimetric analysis, and natural bond orbital analysis sheds light on the structure, bonding, and properties of these complexes. Kinetic profiling across a series of representative reactions reveals reactivity differences that stem from the nature of the ancillary ligand, underscoring the complementary relationships between each pre-catalyst within this toolkit.

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Bis(1,5-cyclooctadiene)nickel(0)

Cited by 14 publications

References 445 publications

A Pharmaceutical Industry Perspective on Sustainable Metal Catalysis

A Pharmaceutical Industry Perspective on Sustainable Metal Catalysis

Directed C–H Functionalization Reactions with a Picolinamide Directing Group: Ni-Catalyzed Cleavage and Byproduct Recycling

Structurally Diverse Bench-Stable Nickel(0) Pre-Catalysts: A Practical Toolkit for In Situ Ligation Protocols

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