We found a match
Your institution may have rights to this item. Sign in to continue.
- Title
The Anionic Pathway in the Nickel‐Catalysed Cross‐Coupling of Aryl Ethers.
- Authors
Borys, Andryj M.; Hevia, Eva
- 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.
- Subjects
ETHERS; OXIDATIVE addition; NUCLEOPHILES
- Publication
Angewandte Chemie, 2021, Vol 133, Issue 46, p24864
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.202110785