Abstract
Fe-cyclopentadienone complexes have been widely utilized in various hydrogenation and dehydrogenation catalytic processes, yet their applications have largely been restricted to non-asymmetric versions. This limitation is primarily due to the considerable challenge of constructing an efficient chiral environment around the active iron center. In this study, we present a structurally distinctive chiral Fe-cyclopentadienone complex with excellent enantiocontrol capabilities. This new iron complex features bulky side arms oriented downward toward the cyclopentadienone plane, which create an ideal chiral environment in front of the catalytically active iron center. It demonstrates excellent performance in the catalytic asymmetric hydrogenation of acylsilanes, exhibiting both high reactivity and selectivity. The broad substrate scope, encompassing aryl-, alkenyl-, and alkyl-acylsilanes, along with successful gram-scale synthesis, underscores its potential applications in pharmaceutical synthesis. Experimental and DFT studies reveal the structural stability and rigidity of the catalyst during catalytic intervals. Additionally, weak interactions between the catalyst and the silyl group in the substrate play a critical role in achieving efficient enantioselectivity. More importantly, this type of chiral iron complex also shows excellent catalytic reactivity and selectivity for asymmetric transfer hydrogenation, utilizing i-PrOH as the hydrogen source.
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Data availability
All data generated and analyzed during this study are included in this Article and its Supplementary Information/Source Data file. Crystallographic data of Fe4 have been deposited at the Cambridge Crystallographic Data Center, under deposition number CCDC 2446024. Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. Data supporting the findings of this manuscript are also available from the corresponding author upon request.
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Acknowledgments
We thank the Hong Kong Research Grants Council (21304324, X.T.), start-up fund from the City University of Hong Kong (Project no 9610667, X.T.), the Guangdong Basic and Applied Basic Research Foundation (2024A1515010323, 2025A1515011907, S.-F.N.), and the open research fund of Songshan Lake Materials Laboratory (2023SLABFN16, S.-F.N.) for financial support. We also thank Dr. Ken Shek Man Yiu in the Chemistry department for assistance in structure determination by X-ray crystallography.
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C.X. performed the experiments and collected the data. B.-X.Y. and S.-F.N. performed the DFT calculations. K.-C.L. provided help for the dimensional NMR test. X.Z. provided suggestions and discussions for the project. C.X. and B.-X.Y. contributed equally to this work. X.T. conceived and directed the project and wrote the paper. All the authors discussed the results and commented on the manuscript.
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X.T. and C.X. are inventors of a patent (U.S. Non-Provisional Utility Patent Application No. 19/370,723). X.T. and C.X. declare no other competing interests. All the other authors have no competing interests to declare.
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Xie, C., Yao, BX., Law, KC. et al. Rationally designed Fe-cyclopentadienone with unique orientations for efficient asymmetric hydrogenation of acylsilanes. Nat Commun (2025). https://doi.org/10.1038/s41467-025-67933-9
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DOI: https://doi.org/10.1038/s41467-025-67933-9
