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The Suzuki Reaction  

Posted on 15. March, 2018.

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Since its discovery in 1979 the Suzuki–Miyaura reaction has come to play a major role in C–C bond formation.

The conventional coupling reaction involves an arylboronic acid, ArB(OH)2, an aryl halide, a base, and a palladium(0) catalyst. Akira Suzuki, Richard Heck and Ei-ichi Negishi were awarded the Nobel Prize in 2010 for their work on novel coupling reactions.1 The accepted mechanism (See Scheme above) involves an oxidative addition of the palladium(0) to the aryl halide to form an organopalladium species from  which the halide is subsequently displaced by a base. In a separate step the second component, the arylboronic acid, forms an 'ate' complex with the base. This then undergoes a transmetallation reaction with the organopalladium species leading to both aryl units becoming attached to the palladium. The cycle is completed by a reductive elimination of palladium(0) and the coupling of the two aryl units.

There have been a number of recent studies on the Suzuki reaction including investigations of the mechanism. Other studies have sought alternative metals to palladium such as nickel and to the nature of the palladium complexes as well as the use of nanoparticles. The selection of the boron reagents, the transmetallation steps as well as the use of water and ionic liquids have received attention. Some of these advances have been reviewed recently.2-5

Various papers which contribute to our knowledge of the Suzuki reaction have appeared in the Journal of Chemical Research in recent years and these illustrate the experimental methods that are used in carrying out the Suzuki reaction. They include the catalysis of the Suzuki and Heck reaction by palladium on carbon nanofibres6 and the use of a fibre-bound palladium(II) complex for the synthesis of arylnaphthalenes.7 The Suzuki coupling of aryl halides with phenylboronic acid catalysed by an amidoxime fibre-nickel(0) complex has been described.8 The use of a PdCl2(1-methylimidazole)2 complex in water9 and microwave-promoted Suzuki reactions10 have also recently received attention.

A number of the papers published in the Journal of Chemical Research reveal aspects of the scope of the reaction. Thus the Suzuki reaction was used in the coupling of aryl units from boronic acids in the synthesis of 2,4-diarylquinolines which were required for spectroscopic studies.11 The development12 of an efficient synthesis of the drug Erismodegib illustrates the importance of carefully selecting the step at which a Suzuki coupling is carried out . The synthesis13 of some diarylethenes for photochromic studies made use of 4-bromo-5-methylthiophene-2-boronic acid and 2-bromopyridine as heterocyclic components in a Suzuki reaction. The structural variety of substrates is also illustrated in a preparation14 of some 4-arylsubstituted thiophene derivatives.

References

1.  A. Suzuki, Angew. Chem. Int. Ed., 2011, 50, 6722-6737.
2 . C.C.C. Johansson Seechum, M.O. Kitching, T.J. Colacot, and V. Snieckus, Angew. Chem. Int. Ed., 2012, 51, 5062-5085.
3.  F.-S. Han, Chem. Soc. Rev., 2013, 42, 5270-5298.
4. A.J.J. Lennox and G.C. Lloyd-Jones, Chem. Soc. Rev., 2014, 43, 412-443.
5. A.J.J. Lennox and G.C. Lloyd-Jones, Angew. Chem. Int. Ed., 2013, 52, 7362-7370.
6.  K. Yamamoto and T. Thiemann, J. Chem. Res., 2011, 35, 246-250.
7 Y.-N. Lu, Z.-C. Wu, Y.-M. Ren, and T.-X. Tao, J. Chem. Res., 2014, 38, 5-8.
8. Z.-C. Wu, Y.- Lu, Y.-M. Ren, Z.-M. Chen, and T.-X. Tao, J. Chem. Res., 2013, 37, 451-454.
9. Y. Li, X.-F. Lin, M.-Y. Liu, L.L. Zhang, H.-P. Jin, and J.-M. Lu, J. Chem. Res., 2013, 37, 294-297.
10. Y.-Q. Zhang, J. Chem. Res., 2013, 37, 375-376.
11. A.O. Adeloya and M.J. Mphahlele, J. Chem. Res., 2014, 38, 254-259.
12. B. Hu, J. Cai, J. Chen, M. Cao, P. Wang, X. Zong, R. Zhang, and M. Ji,  J. Chem. Res., 2014, 38, 18-20.
13. C. Fan, S. Cui, S. Cu, Q. Huang, and G. Liu, J. Chem. Res., 2013, 37, 574-578
14. Z.Z. Xu, D. Yu, and M. Yu, J. Chem. Res., 2013, 37, 441-443.