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Further Information

Related Reactions
Grignard Reaction
Negishi Coupling
Suzuki Coupling
Stille Coupling

Kumada Coupling

The Kumada Coupling was the first Pd or Ni-catalyzed cross coupling reaction, developed in 1972.

The coupling of Grignard reagents with alkyl, vinyl or aryl halides under Ni-catalysis provides an economic transformation, but the reaction is limited to halide partners that do not react with organomagnesium compounds. One example is in the industrial-scale production of styrene derivatives, and the Kumada Coupling is the method of choice for the low-cost synthesis of unsymmetrical biaryls.

The advantage of this reaction is the direct coupling of Grignard reagents, which avoids additional reaction steps such as the conversion of Grignard reagents to zinc compounds for the starting materials in the Negishi Coupling.

Mechanism of the Kumada Coupling

Recent Literature

Hydroxyphosphine Ligand for Nickel-Catalyzed Cross-Coupling through Nickel/Magnesium Bimetallic Cooperation
N. Yoshikai, H. Matsuda, E. Nakamura, J. Am. Chem. Soc., 2009, 131, 9590-9599.

Amido Pincer Nickel Catalyzed Kumada Cross-Coupling of Aryl, Heteroaryl, and Vinyl Chlorides
X.-Q. Zhang, Z.-X. Wang, Synlett, 2013, 24, 2081-2084.

Kumada Coupling of Aryl, Heteroaryl, and Vinyl Chlorides Catalyzed by Amido Pincer Nickel Complexes
N. Liu, Z.-X. Wang, J. Org. Chem., 2011, 76, 10031-10032.

Cross-Coupling of ArX with ArMgBr Catalyzed by N-Heterocyclic Carbene-Based Nickel Complexes
W.-J. Guo, Z.-X. Wang, J. Org. Chem., 2013, 78, 1054-1061.

Phosphinous Acid-Catalyzed Cross-Coupling of Aryl Halides and Aryl Grignards
C. Wolf, H. Xu, J. Org. Chem., 2008, 73, 162-167.

Magnesiation of Electron-Rich Aryl Bromides and Their Use in Nickel-Catalyzed Cross-Coupling Reactions
S. Y. W. Lau, G. Hughes, P. D. O'Shea, I. W. Davies, Org. Lett., 2007, 9, 2239-2242.

Room-Temperature Kumada Cross-Coupling of Unactivated Aryl Chlorides Catalyzed by N-Heterocylic Carbene-Based Nickel(II) Complexes
Z. Xi, B. Liu, W. Chen, J. Org. Chem., 2008, 73, 3954-3957.

Bidentate P, N-P Ligand for Nickel-Catalyzed Cross-Coupling of Aryl or Benzyl Chlorides with ArMgX
R. Ghosh, A. Sarkar, J. Org. Chem., 2010, 75, 8283-8386.

Kumada-Tamao-Corriu Coupling of Heteroaromatic Chlorides and Aryl Ethers Catalyzed by (IPr)Ni(allyl)Cl
M. J. Iglesias, A. Prueto, M. C. Nicasio, Org. Lett., 2012, 14, 4318-4321.

Biaryl Construction through Kumada Coupling with Diaryl Sulfates as One-by-One Electrophiles under Mild Conditions
B.-T. Guan, X.-Y. Lu, Y. Zheng, D.-G. Yu, T. Wu, K.-L. Li, B.-J. Li, Z.-J. Shi, Org. Lett., 2010, 12, 396-399.

Stereoretentive Pd-Catalyzed Kumada-Corriu Couplings of Alkenyl Halides at Room Temperature
A. L. Krasovskiy, S. Haley, K. Voigtritter, B. H. Lipshutz, Org. Lett., 2014, 16, 4066-4069.

Air-Stable Secondary Phosphine Oxide or Chloride (Pre)Ligands for Cross-Couplings of Unactivated Alkyl Chlorides
L. Ackermann, A. R. Kapdi, C. Schulzke, Org. Lett., 2010, 12, 2298-2301.

Palladium-Catalyzed Cross-Coupling Reaction of Secondary Benzylic Bromides with Grignard Reagents
A. López-Pérez, J. Adrio, J. C. Carretero, Org. Lett., 2009, 11, 5514-5517.

Palladium-Catalyzed Coupling of Alkyl Chlorides and Grignard Reagents
A. C. Frisch, N. Shaikh, A. Zapf, M. Beller, Angew. Chem., 2002, 114, 4218-4221.

Nickel-Catalyzed Kumada Cross-Coupling Reactions of Tertiary Alkylmagnesium Halides and Aryl Bromides/Triflates
A. Joshi-Pangu, C.-Y. Wang, M. R. Biscoe, J. Am. Chem. Soc., 2011, 133, 8478-8481.

Air-Stable PinP(O)H as Preligand for Palladium-Catalyzed Kumada Couplings of Unactivated Tosylates
L. Ackermann, A. Althammer, Org. Lett., 2006, 8, 3457-3460.

Room Temperature Palladium-Catalyzed Cross Coupling of Aryltrimethylammonium Triflates with Aryl Grignard Reagents
J. T. Reeves, D. R. Fandrick, Z. Tan, J. J. Song, H. Lee, N. K. Yee, C. H. Senanayake, Org. Lett., 2010, 12, 4388-4391.

Nickel-Catalyzed Cross-Coupling Reaction of Aryl Fluorides and Chlorides with Grignard Reagents under Nickel/Magnesium Bimetallic Cooperation
N. Yoshikai, H. Mashima, E. Nakamura, J. Am. Chem. Soc., 2005, 127, 17978-17979.

Kumada-Corriu Reactions of Alkyl Halides with Alkynyl Nucleophiles
L.-M. Yang, L.-F. Huang, T.-Y. Luh, Org. Lett., 2004, 6, 1461-1463.