Fifty years ago, Kochi reported the iron-catalysed cross-coupling of alkenyl halides and alkyl Grignard reagents. Sparking a cross-coupling revolution, we reflect on the impact of this achievement and the importance of iron in the development of cross-coupling catalysis.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 per month
cancel any time
Subscribe to this journal
Receive 12 digital issues and online access to articles
$119.00 per year
only $9.92 per issue
Rent or buy this article
Get just this article for as long as you need it
$39.95
Prices may be subject to local taxes which are calculated during checkout

References
Johansson Seechurn, C. C. C., Kitching, M. O., Colacot, T. J. & Snieckus, V. Palladium-catalyzed cross-coupling: a historical contextual perspective to the 2010 Nobel Prize. Angew. Chem. Int. Ed. 51, 5062–5085 (2012).
Tamura, M. & Kochi, J. K. Vinylation of Grignard reagents. Catalysis by iron. J. Am. Chem. Soc. 93, 1487–1489 (1971).
Kharasch, M. S. & Fields, E. K. Factors determining the course and mechanisms of Grignard reactions. IV. The effect of metallic halides on the reaction of aryl Grignard reagents and organic halides. J. Am. Chem. Soc. 63, 2316–2320 (1941).
Smith, R. S. & Kochi, J. K. Mechanistic studies of iron catalysis in the cross coupling of alkenyl halides and Grignard reagents. J. Org. Chem. 41, 502–509 (1976).
Neidig, M. L. et al. Development and evolution of mechanistic understanding in iron-catalyzed cross-coupling. Acc. Chem. Res. 52, 140–150 (2019).
Muñoz, S. B. III, Daifuku, S. L., Brennessel, W. W. & Neidig, M. L. Isolation, characterization, and reactivity of Fe8Me12–: Kochi’s S = 1/2 species in iron-catalyzed cross-couplings with MeMgBr and ferric salts. J. Am. Chem. Soc. 138, 7492–7495 (2016).
Cahiez, G. & Avedissian, H. Highly stereo- and chemoselective iron-catalyzed alkenylation of organomagnesium compounds. Synthesis 8, 1199–1205 (1998).
Fürstner, A. & Leitner, A. Iron-catalyzed cross-coupling reactions of alkyl-Grignard reagents with aryl chlorides, tosylates, and triflates. Angew. Chem. Int. Ed. 41, 609–612 (2002).
Nakamura, M., Matsuo, K., Ito, S. & Nakamura, E. Iron-catalyzed cross-coupling of primary and secondary alkyl halides with aryl Grignard reagents. J. Am. Chem. Soc. 126, 3686–3687 (2004).
Bedford, R. B. et al. Iron–phosphine, –phosphite, –arsine, and –carbene catalysts for the coupling of primary and secondary alkyl halides with aryl Grignard reagents. J. Org. Chem. 71, 1104–1110 (2006).
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing interests.
Rights and permissions
About this article
Cite this article
Neate, P.G.N., Neidig, M.L. Forged in iron. Nat Rev Chem 5, 223–224 (2021). https://doi.org/10.1038/s41570-021-00259-4
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41570-021-00259-4