Negishi Coupling

The Negishi Coupling, published in 1977, was the first reaction that allowed the preparation of unsymmetrical biaryls in good yields. The versatile nickel- or palladium-catalyzed coupling of organozinc compounds with various halides (aryl, vinyl, benzyl, or allyl) has broad scope, and is not restricted to the formation of biaryls.

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Mechanism

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Recent Literature

An Extremely Active Catalyst for the Negishi Cross-Coupling Reaction
J. E. Milne, S. L. Buchwald, J. Am. Chem. Soc., 2004, 126, 13028-13032.

The First Negishi Cross-Coupling Reaction of Two Alkyl Centers Utilizing a Pd-N-Heterocyclic Carbene (NHC) Catalyst
N. Hadei, E. A. B. Kantchev, C. J. O'Brien, M. G. Organ, Org. Lett., 2005, 7, 3805-3807.

Highly Efficient, General Procedure for the Preparation of Alkylzinc Reagents from Unactivated Alkyl Bromides and Chlorides
S. Huo, Org. Lett., 2003, 5, 423-425.

Palladium-Catalyzed Negishi Cross-Coupling Reactions of Unactivated Alkyl Iodides, Bromides, Chlorides, and Tosylates
J. Zhou, G. C. Fu, J. Am. Chem. Soc., 2003, 125, 12527-12530.

Catalytic Enantioselective Negishi Reactions of Racemic Secondary Benzylic Halides
F. O. Arp, G. C. Fu, J. Am. Chem. Soc., 2005, 127, 10482-10483.

Synthesis of the Precursor of Anti-Inflammatory Agents by Cross-Coupling Using Electrogenerated Highly Reactive Zinc
A. A. Jalil, N. Kurono, M. Tokuda, Synthesis, 2002, 2681-2686.

Synthesis of Substituted 2,2'-Bipyridines from 2-Bromo- or 2-Chloropyridines Using Tetrakis(triphenylphosphine)palladium(0) as a Catalyst in a Modified Negishi Cross-Coupling Reaction
U. Kiehne, J. Bunzen, H. Staats, A. Lützen, Synthesis, 2007, 1061-1069.

Enantioselective, Palladium-Catalyzed α-Arylation of N-Boc-pyrrolidine
K. R. Campos, A. Klapars, J. H. Waldman, P. G. Dormer, C.-Y. Chen, J. Am. Chem. Soc., 2006, 128, 3538-3539.