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Iron-catalysed alkenylzincation of allenes via electrophilicity reversal

Nature Catalysis volume 8, pages 178–186 (2025)Cite this article

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Abstract

Given the structural characteristics of allenes, nucleophilic additions usually occur at the electron-deficient central carbon atom of allene. Here we report an iron-catalysed alkenylzincation reaction of terminal allenes that shows abnormal regioselectivity, wherein the electrophilic zinc moiety from an organozinc reagent is incorporated at the electron-deficient central carbon atom of the allene. This alkenylzincation reaction shows broad functional group compatibility and excellent regio- and stereoselectivities. Using this method, we accessed cis-1,4-dienylzinc reagents and their corresponding polysubstituted 1,4-diene derivatives, which are notoriously challenging to prepare via conventional routes. Mechanistic studies revealed that an unexpected reversal of the electrophilicity of the allene carbons is realized through the electron donation from the Fe(0) to the allene via π back-bonding, resulting in the observed abnormal regioselectivity.

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Fig. 1: Catalytic alkenylzincation of terminal allenes.
Fig. 2: Substrate scope of monosubstituted and disubstituted allenes.
Fig. 3: Substrate scope of substituted alkenylzinc reagents.
Fig. 4: Synthetic applications of the iron-catalysed vinylzincation of terminal allenes.
Fig. 5: Mechanistic studies.

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Data availability

The data supporting the findings of this study are available within the Article and its Supplementary Information or from the authors upon reasonable request. Crystallographic data for the structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2293033. Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/.

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Acknowledgements

We thank the National Key R&D Program of China (2021YFA1500200), National Natural Science Foundation of China (22301230, 22221002 and 92256301), Haihe Laboratory of Sustainable Chemical Transformations, Fundamental Research Funds for the Central Universities and New Cornerstone Science Foundation through the XPLORER PRIZE for financial support.

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Authors and Affiliations

  1. Frontiers Science Center for New Organic Matter, the State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin, China

    Jun-Jia Chen, Mu-Han Guan, Peng He, Ming-Yao Huang, Xin-Yu Zhang & Shou-Fei Zhu

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  1. Jun-Jia Chen
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Contributions

S.-F.Z. supervised the project. S.-F.Z. and J.-J.C. conceived the idea. J.-J.C. and M.-H.G. designed and carried out the experiments. M.-H.G. and P.H. designed and performed the DFT studies. J.-J.C., M.-H.G., P.H., M.-Y.H. and X.-Y.Z. analysed data. All authors discussed the results and contributed to writing the manuscript.

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Correspondence to Shou-Fei Zhu.

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Supplementary Information

Supplementary Notes, Methods and Tables 1–12.

Supplementary Data 1

Crystallographic data of T11.

Supplementary Data 2

CIF (Crystallographic Information File) report of T11.

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Chen, JJ., Guan, MH., He, P. et al. Iron-catalysed alkenylzincation of allenes via electrophilicity reversal. Nat Catal 8, 178–186 (2025). https://doi.org/10.1038/s41929-025-01293-x

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