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Abstract This work demonstrates the dominance of a Ni(0/II/III) cycle for Ni‐photoredox amide arylation, which contrasts with other Ni‐photoredox C‐heteroatom couplings that operate via Ni(I/III) self‐sustained cycles. The kinetic data gathered when using different Ni precatalysts supports an initial Ni(0)‐mediated oxidative addition into the aryl bromide. Using NiCl2as the precatalyst resulted in an observable induction period, which was found to arise from a photochemical activation event to generate Ni(0) and to be prolonged by unproductive comproportionation between the Ni(II) precatalyst and the in situ generated Ni(0) active species. Ligand exchange after oxidative addition yields a Ni(II) aryl amido complex, which was identified as the catalyst resting state for the reaction. Stoichiometric experiments showed that oxidation of this Ni(II) aryl amido intermediate was required to yield functionalized amide products. The kinetic data presented supports a rate‐limiting photochemically‐mediated Ni(II/III) oxidation to enable C−N reductive elimination. An alternative Ni(I/III) self‐sustained manifold was discarded based on EPR and kinetic measurements. The mechanistic insights uncovered herein will inform the community on how subtle changes in Ni‐photoredox reaction conditions may impact the reaction pathway, and have enabled us to include aryl chlorides as coupling partners and to reduce the Ni loading by 20‐fold without any reactivity loss.
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Leveraging the Redox Promiscuity of Nickel To Catalyze C–N Coupling Reactions
This perspective details advances made in the field of Ni-catalyzed C–N bond formation. The use of this Earth abundant metal to decorate amines, amides, lactams, and heterocycles enables direct access to a variety of biologically active and industrially relevant compounds in a sustainable manner. Herein, different strategies that leverage the propensity of Ni to facilitate both one- and two-electron processes will be surveyed. The first part of this Perspective focuses on strategies that facilitate C–N couplings at room temperature by accessing oxidized Ni(III) intermediates. In this context, advances in photochemical, electrochemical, and chemically mediated processes will be analyzed. A special emphasis has been put on providing a comprehensive explanation of the different mechanistic avenues that have been proposed to facilitate these chemistries; either Ni(I/III) self-sustained cycles or Ni(0/II/III) photochemically mediated pathways. The second part of this Perspective details the ligand designs that also enable access to this reactivity via a two-electron Ni(0/II) mechanism. Finally, we discuss our thoughts on possible future directions of the field.
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- Award ID(s):
- 2235778
- PAR ID:
- 10486616
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- The Journal of Organic Chemistry
- ISSN:
- 0022-3263
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.joc.3c02353
