The Anionic Pathway in the Nickel‐Catalysed Cross‐Coupling of Aryl Ethers

Autor: Eva Hevia, Andryj M. Borys
Jazyk: angličtina
Rok vydání: 2021
Předmět:
Zdroj: 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
ISSN: 1521-3773
1433-7851
DOI: 10.1002/anie.202110785
Popis: 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.
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.
Databáze: OpenAIRE
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