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Hiyama Coupling
Kumada Coupling
Suzuki Coupling
Stille Coupling

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.

Mechanism of the Negishi Coupling

Recent Literature

Mild Negishi Cross-Coupling Reactions Catalyzed by Acenaphthoimidazolylidene Palladium Complexes at Low Catalyst Loadings
Z. Liu, N. Dong, M. Xu, Z. Sun, T. Tu, J. Org. Chem., 2013, 78, 7436-7444.

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

One-Pot Negishi Cross-Coupling Reactions of In Situ Generated Zinc Reagents with Aryl Chlorides, Bromides, and Triflates
S. Sase, M. Jaric, A. Metzger, V. Malakhov, P. Knochel, J. Org. Chem., 2008, 73, 7380-7382.

Efficient Negishi Coupling Reactions of Aryl Chlorides Catalyzed by Binuclear and Mononuclear Nickel-N-Heterocyclic Carbene Complexes
Z. Xi, Y. Zhou, W. Chen, J. Org. Chem., 2008, 73, 8497-8501.

The First General Method for Palladium-Catalyzed Negishi Cross-Coupling of Aryl and Vinyl Chlorides:  Use of Commercially Available Pd(P(t-Bu)3)2 as a Catalyst
C. Dai, G. C. Fu, J. Am. Chem. Soc., 2001, 123, 2719-2724.

Cross-Coupling of Aryltrimethylammonium Iodides with Arylzinc Reagents Catalyzed by Amido Pincer Nickel Complexes
X.-Q. Zhang, Z.-X. Wang, J. Org. Chem., 2012, 77, 3658-3663.

New Efficient Preparation of Arylzinc Compounds from Aryl Halides Using Cobalt Catalysis and Sacrificial Anode Process
C. Gosmini, Y. Rollin, J. Y. Nédélec, J. Périchon, J. Org. Chem., 2000, 65, 6024-6026.

Copper-Catalyzed Negishi Coupling of Diarylzinc Reagents with Aryl Iodides
S. Thapa, A. S. Vangala, R. Giri, Synthesis, 2016, 48, 504-511.

POxAP Precatalysts and the Negishi Cross-Coupling Reaction
S.-Q. Tang, M. Schmitt, F. Bihel, Synthesis, 2020, 52, 51-59.

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.

Stereospecific Transformations of Alkylboronic Esters Enabled by Direct Boron-to-Zinc Transmetalation
H. Liang, J. P. Morken, J. Am. Chem. Soc., 2023, 145, 9976-9981.

Negishi Coupling of Secondary Alkylzinc Halides with Aryl Bromides and Chlorides
C. Han, S. L. Buchwald, J. Am. Chem. Soc., 2009, 131, 7532-7533.

Effective Pd-Nanoparticle (PdNP)-Catalyzed Negishi Coupling Involving Alkylzinc Reagents at Room Temperature
J. Liu, Y. Deng, H. Wang, H. Zhang, G. Yu, B. Wu, H. Zhang, Q. Li, T. B. Marder, Z. Yang, A. Lei, Org. Lett., 2008, 10, 2661-2664.

Nickel-Catalyzed Asymmetric Negishi Cross-Couplings of Secondary Allylic Chlorides with Alkylzincs
S. Son, G. C. Fu, J. Am. Chem. Soc., 2008, 130, 2756-2757.

Efficient Cross-Coupling of Aryl Chlorides with Arylzinc Reagents Catalyzed by Amido Pincer Complexes of Nickel
L. Wang, Z.-X. Wang, Org. Lett., 2007, 9, 4335-4338.

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

Zn-Mediated, Pd-Catalyzed Cross-Couplings in Water at Room Temperature Without Prior Formation of Organozinc Reagents
A. Krasovskiy, C. Duplais, B. H. Lipshutz, J. Am. Chem. Soc., 2009, 131, 15592-15593.

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.

Nickel-Catalyzed Negishi Cross-Coupling Reactions of Secondary Alkylzinc Halides and Aryl Iodides
A. Joshi-Pangu, M. Ganesh, M. R. Biscoe, Org. Lett., 2011, 13, 1218-1221.

Superior Effect of a π-Acceptor Ligand (Phosphine−Electron-Deficient Olefin Ligand) in the Negishi Coupling Involving Alkylzinc Reagents
X. Luo, H. Zhang, H. Duan, Q. Liu, L. Zhu, T. Zhang, A. Lei, Org. Lett., 2007, 9, 4571-4574.

Highly Selective Reactions of Unbiased Alkenyl Halides and Alkylzinc Halides: Negishi-Plus Couplings
A. Krasovskiy, B. H. Lipshutz, Org. Lett., 2011, 13, 3822-3825.

Ligand Effects on Negishi Couplings of Alkenyl Halides
A. Krasovskiy, B. H. Lipshutz, Org. Lett., 2011, 13, 3818-3821.

A nonionic amphiphile enables a simple approach to Pd-catalyzed stereoselective sp3-sp2 cross-couplings between alkyl and alkenyl bromides in the presence of zinc powder in water to give coupled products in good yields without prior formation of the organozinc reagents. The reaction is conducted at room temperature and tolerates various functional groups.
A. Krasovskiy, C. Duplais, B. H. Lipshutz, Org. Lett., 2010, 12, 4742-4744.

Iron-Catalyzed Negishi Coupling Toward an Effective Olefin Synthesis
T. Niu, W. Zhang, D. Huang, C. Xu, H. Wang, Y. Hu, Org. Lett., 2009, 11, 4474-4477.

Highly Regio- and Stereoselective Synthesis of (Z)-Trisubstituted Alkenes via Propyne Bromoboration and Tandem Pd-Catalyzed Cross-Coupling
C. Wang, T. Tobrman, Z. Xu, E.-i. Negishi, Org. Lett., 2009, 11, 4092-4095.

Highly Regioselective Synthesis of Trisubstituted Allenes via Lithiation of 1-Aryl-3-alkylpropadiene, Subsequent Transmetalation, and Pd-Catalyzed Negishi Coupling Reaction
J. Zhao, Y. Liu, S. Ma, Org. Lett., 2008, 10, 1521-1523.

Highly Satisfactory Procedures for the Pd-Catalyzed Cross Coupling of Aryl Electrophiles with in Situ Generated Alkynylzinc Derivatives
L. Anastasia, E.-i. Negishi, Org. Lett., 2001, 3, 3111-3113.

A Strictly "Pair"-Selective Synthesis of Conjugated Diynes via Pd-Catalyzed Cross Coupling of 1,3-Diynylzincs:  A Superior Alternative to the Cadiot-Chodkiewicz Reaction
E.-i. Negishi, M. Hata, C. Xu, Org. Lett., 2000, 2, 3687-3689.

One-Pot Formation and Derivatization of Di- and Triynes Based on the Fritsch-Buttenberg-Wiechell Rearrangement
T. Luu, Y. Morisaki, N. Cunningham, R. R. Tykwinski, J. Org. Chem., 2007, 72, 9622-9629.

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.

General, Robust, and Stereocomplementary Preparation of β-Ketoester Enol Tosylates as Cross-Coupling Partners Utilizing TsCl-N-Methylimidazole Agents
H. Nakatsuji, K. Ueno, T. Misaki, Y. Tanabe, Org. Lett., 2008, 10, 2131-2134.

High Temperature Metalation of Functionalized Aromatics and Heteroaromatics using (tmp)2Znˇ2MgCl2ˇ2LiCl and Microwave Irradiation
S. Wunderlich, P. Knochel, Org. Lett., 2008, 10, 4705-4707.

A Mild Negishi Cross-Coupling of 2-Heterocyclic Organozinc Reagents and Aryl Chlorides
M. R. Luzung, J. S. Patel, J. Yin, J. Org. Chem., 2010, 75, 8330-8332.

Nickel-Catalyzed Negishi Alkylations of Styrenyl Aziridines
C.-Y. Huang, A. G. Doyle, J. Am. Chem. Soc., 2012, 134, 9541-9544.

Synthesis of Substituted Cyclopropanecarboxylates via Room Temperature Palladium-Catalyzed α-Arylation of Reformatsky Reagents
S. N. Greszler, G. T. Halvorsen, E. A. Voight, Org. Lett., 2017, 19, 2490-2493.

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.

Palladium-Catalyzed Cross-Coupling of Silyl Electrophiles with Alkylzinc Halides: A Silyl-Negishi Reaction
A. P. Cinderella, B. Vulovic, D. A. Watson, J. Am. Chem. Soc., 2017, 139, 7741-7744.

Nickel-Catalyzed Negishi Cross-Coupling of Alkyl Halides, Including Unactivated Tertiary Halides, with a Boron-Stabilized Organozinc Reagent
P. Guo, H. Jin, J. Han, L. Xu, P. Li, M. Zhan, Org. Lett., 2023, 25, 1246-1251.

Palladium-Catalyzed Chemoselective Negishi Cross-Coupling of Bis[(pinacolato)boryl]methylzinc Halides with Aryl (Pseudo)Halides
H. Lee, Y. Lee, S. H. Cho, Org. Lett., 2019, 21, 5912-5916.