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Design, synthesis and visible-light-induced non-radical reactions of dual-functional Rh catalysts

Nature Synthesis volume 2, pages 535–547 (2023)Cite this article

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Abstract

Transition metal photo-induced catalysts operating in a single catalytic cycle are preferable compared with binary catalytic systems comprising both transition metal and photoredox catalysts. Such single-catalyst systems perform the dual function of visible light absorption and chemical transformation. However, most visible-light-driven catalytic reactions proceed via radical mechanisms, limiting the reaction types to which the catalysts are applicable. Several non-radical catalytic reactions have been developed, but these reactions are substrate dependent owing to the low visible-light-harvesting ability of the catalysts. Here we report the design, synthesis and visible-light-induced non-radical reactions of dual-functional Rh catalysts, spiro-fluorene-indenoindenyl (SFI)-Rh(I) complexes. The SFI-Rh(I) complexes with non-fused but π-extended ligands reduce substrate dependence owing to high visible-light-harvesting ability, and show high stability due to resistance against protonation. Thus, the SFI-Rh(I) catalysts extend the scope of typical Rh(I)-catalysed reactions, such as the C–H borylation of arenes and [2+2+2] cycloaddition of alkynes, to challenging substrates under blue light-emitting diode irradiation at room temperature.

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Fig. 1: Overview of previous studies and this work.
Fig. 2: Au(I)-catalysed triple cyclization of tetraaryl-1,5-diynes.
Fig. 3: Synthesis and characterization of SFI-Rh(I) complexes.
Fig. 4: Theoretical mechanistic studies of photoinduced C–H borylation of arenes.
Fig. 5: Theoretical mechanistic studies of photoinduced [2+2+2] cycloaddition.

Data availability

The data that support the findings of this study are available in this article and Supplementary Information (experimental procedures and characterization data). Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2123980 (2j), CCDC 2210844 (3m) and CCDC 2210843 (3n). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/.

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Acknowledgements

This research was supported partly by JSPS KAKENHI grant nos JP21K14623 (to Y.N.) and JP19H00893 (to K.T.) and JP22H05346 in Transformative Research Areas (A) JP21A204 Digitalization-driven Transformative Organic Synthesis (Digi-TOS) (to Y.N.). This research was also supported partly by grants from Fukuoka Naohiko Memorial Foundation, Uehara Memorial Foundation and UBE Foundation (to Y.N.). We thank Umicore for the support in supplying the Rh complexes. Allotment of computational resources from TSUBAME (Tokyo Institute of Technology) is gratefully acknowledged.

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Authors and Affiliations

  1. Department of Chemical Science and Engineering, Tokyo Institute of Technology, Tokyo, Japan

    Seiya Ouchi, Tomonori Inoue, Juntaro Nogami, Yuki Nagashima & Ken Tanaka

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  1. Seiya Ouchi
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Contributions

S.O., Y.N. and K.T. conceived and designed the experiments. S.O., T.I. and Y.N. conducted experiments. Y.N. conducted computational studies. J.N. performed the X-ray crystal structure analysis. Y.N. and K.T. directed the project and wrote the paper. All authors participated in data analyses and discussions.

Corresponding authors

Correspondence to Yuki Nagashima or Ken Tanaka.

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Nature Synthesis thanks Edward Anderson, Chunhua Hu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Thomas West, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Materials and methods, synthetic experiments, single-crystal X-ray diffraction analysis of 2j, 3m and 3n, computational studies, NMR spectra, UV–vis absorption data and references, Supplementary Figs. 1–17 and Tables 1–9.

Supplementary Data 1

Crystallographic data for 2j (CCDC 2123980).

Supplementary Data 2

Crystallographic data for 3m (CCDC 2210844).

Supplementary Data 3

Crystallographic data for 3n (CCDC 2210843).

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Ouchi, S., Inoue, T., Nogami, J. et al. Design, synthesis and visible-light-induced non-radical reactions of dual-functional Rh catalysts. Nat. Synth 2, 535–547 (2023). https://doi.org/10.1038/s44160-023-00268-9

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