Negishi E.
*
King AO,
Okukado N.
Purdue University, West Lafayette, USA
Selective Carbon–Carbon Bond Formation via Transition Metal Catalysis. 3. A Highly
Selective Synthesis of Unsymmetrical Biaryls and Diarylmethanes by the Nickel- or
Palladium-Catalyzed Reaction of Aryl- and Benzylzinc Derivatives with Aryl Halides.
J. Org. Chem. 1977;
42: 1821-1823
Key words
palladium catalysis - nickel catalysis - organozinc reagents - Negishi coupling
Significance
In 1977, Negishi and co-workers described the first transition-metal-catalyzed cross-coupling
using aryl- and benzylzinc reagents with substituted aryl halides. Two catalytic systems
using either nickel or palladium salts in combination with PPh3 were developed leading to the coupling products in high yields.
Comment
In comparison to the corresponding magnesium-based organometallics, the use of organozinc
species enables the coupling of aryl halides bearing sensitive functional moieties,
such as ester, nitrile, or even nitro groups. Due to the low toxicity of organozinc
reagents, and the mild conditions required for the cross-coupling, their application
in academic and industrial research remains a growing field.
Review
D. Haas, J. M. Hammann, R. Greiner, P. Knochel ACS Catal.
2016, 6, 1540–1552.
