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Stepwise on-demand functionalization of multihydrosilanes enabled by a hydrogen-atom-transfer photocatalyst based on eosin Y

Nature Chemistry volume 15, pages 666–676 (2023)Cite this article

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Abstract

Organosilanes are of vital importance for modern human society, having found widespread applications in functional materials, organic synthesis, drug discovery and life sciences. However, their preparation remains far from trivial, and on-demand synthesis of heteroleptic substituted silicon reagents is a formidable challenge. The generation of silyl radicals from hydrosilanes via direct hydrogen-atom-transfer (HAT) photocatalysis represents the most atom-, step-, redox- and catalyst-economic pathway for the activation of hydrosilanes. Here, in view of the green characteristics of neutral eosin Y (such as its abundance, low cost, metal-free nature, absorption of visible light and excellent selectivity), we show that using it as a direct HAT photocatalyst enables the stepwise custom functionalization of multihydrosilanes, giving access to fully substituted silicon compounds. By exploiting this strategy, we realize preferable hydrogen abstraction of Si–H bonds in the presence of active C–H bonds, diverse functionalization of hydrosilanes (for example, alkylation, vinylation, allylation, arylation, deuteration, oxidation and halogenation), and remarkably selective monofunctionalization of di- and trihydrosilanes.

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Fig. 1: Neutral eosin Y-catalysed functionalization of hydrosilanes.
Fig. 2: Synthetic applications of functional silanes generated from eosin Y-promoted HAT photocatalysis.

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Data availability

The authors declare that all data supporting the findings of this study are available within the Article and its Supplementary Information. Computational raw data are available at https://doi.org/10.6084/m9.figshare.20154056.

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Acknowledgements

We acknowledge financial support provided by the Ministry of Education (MOE) of Singapore (MOET2EP10120-0014, J.W.; MOET2EP10120-0007, X.L.), the National University of Singapore (R-143-000-B60-114, J.W.) and the National Natural Science Foundation of China (21688102, G.C.). We thank D. Ravelli (University of Pavia) for insightful discussions.

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  1. These authors contributed equally: Xuanzi Fan, Muliang Zhang.

Authors and Affiliations

  1. Department of Chemistry, National University of Singapore, Singapore, Republic of Singapore

    Xuanzi Fan, Muliang Zhang, Qi Zhou, Yanbin Zhang, Jiajia Yu, Wengang Xu, Jianming Yan, Haiwang Liu, Zhexuan Lei, Yan Chong Ter & Jie Wu

  2. Key Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing, People’s Republic of China

    Yuanjun Gao & Ganglong Cui

  3. Fluorescence Research Group, Singapore University of Technology and Design, Singapore, Republic of Singapore

    Supphachok Chanmungkalakul & Xiaogang Liu

  4. Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore, Republic of Singapore

    Yanwei Lum

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Contributions

X.F. and M.Z. contributed equally to the work; their names are listed alphabetically by family name. J.W. conceived the project and directed the research. X.F. and M.Z. designed and performed the experiments. Y.G. and G.C. performed the DFT calculations. Y.L. performed the GC-MS analysis for H2 source investigation. X.F., M.Z., Q.Z., Y.Z., J. Yu, H.L., W.X., Y.C.T., J. Yan and S.C. conducted experiments to demonstrate the substrate scope. J.W., X.F., M.Z., Z.L., Y.G. and G.C. wrote the paper. All authors commented on the final paper and contributed to the analysis and interpretation of the results.

Corresponding author

Correspondence to Jie Wu.

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Competing interests

J.W., F.X. and M.Z. are inventors on an International Patent Application (PCT/SG2022/050462) submitted by the National University of Singapore that covers the synthesis of functional silanes from multihydrosilanes by neutral eosin Y HAT photocatalysis. The other authors declare no competing interests.

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Nature Chemistry thanks Junha Jeon, Paul Rablen and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–64, Tables 1–31, synthetic procedural details, mechanistic studies, proposed mechanisms, high-resolution mass spectrometry, IR data, NMR data and spectra.

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Cartesian coordinates of computational structures.

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Fan, X., Zhang, M., Gao, Y. et al. Stepwise on-demand functionalization of multihydrosilanes enabled by a hydrogen-atom-transfer photocatalyst based on eosin Y. Nat. Chem. 15, 666–676 (2023). https://doi.org/10.1038/s41557-023-01155-8

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