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.

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Mechanism of the Kumada Coupling

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Recent Literature

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.

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

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.

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.