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The Anionic Pathway in the Nickel‐Catalysed Cross‐Coupling of Aryl Ethers
- Source :
- Angewandte Chemie (International Ed. in English), Borys, Andryj M.; Hevia, Eva (2021). The Anionic Pathway in the Nickel-Catalysed Cross-Coupling of Aryl Ethers. Angewandte Chemie (International ed.), 60(46), pp. 24659-24667. Wiley-VCH 10.1002/anie.202110785
- Publication Year :
- 2021
- Publisher :
- John Wiley and Sons Inc., 2021.
-
Abstract
- The Ni‐catalysed cross‐coupling of aryl ethers is a powerful method to forge new C−C and C−heteroatom bonds. However, the inert C(sp2)−O bond means that a canonical mechanism that relies on the oxidative addition of the aryl ether to a Ni0 centre is thermodynamically and kinetically unfavourable, which suggests that alternative mechanisms may be involved. Here, we provide spectroscopic and structural insights into the anionic pathway, which relies on the formation of electron‐rich hetero‐bimetallic nickelates by adding organometallic nucleophiles to a Ni0 centre. Assessing the rich co‐complexation chemistry between Ni(COD)2 and PhLi has led to the structures and solution‐state chemistry of a diverse family of catalytically competent lithium nickelates being unveiled. In addition, we demonstrate dramatic solvent and donor effects, which suggest that the cooperative activation of the aryl ether substrate by Ni0‐ate complexes plays a key role in the catalytic cycle.<br />Assessment of the rich co‐complexation chemistry of Ni(COD)2 and PhLi has led to a new family of structurally diverse lithium nickelates being uncovered. Combined stoichiometric, catalytic, and kinetic studies reveal that these hetero‐bimetallic complexes may be the key intermediates that facilitate the smooth C−O bond cleavage and cross‐coupling of aryl ethers under mild conditions.
- Subjects :
- catalysis
organolithium
Aryl
Substrate (chemistry)
Ether
General Chemistry
General Medicine
Oxidative addition
Combinatorial chemistry
Catalysis
Solvent
chemistry.chemical_compound
nickel
Nucleophile
chemistry
Catalytic cycle
Cross‐Coupling Reactions | Very Important Paper
540 Chemistry
cross-coupling
570 Life sciences
biology
hetero-bimetallic compounds
Research Articles
Research Article
Subjects
Details
- Language :
- English
- ISSN :
- 15213773 and 14337851
- Volume :
- 60
- Issue :
- 46
- Database :
- OpenAIRE
- Journal :
- Angewandte Chemie (International Ed. in English)
- Accession number :
- edsair.doi.dedup.....a8ffd4aa8162af16e05bd291bd566ce9
- Full Text :
- https://doi.org/10.1002/anie.202110785