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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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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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.
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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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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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