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Chiral paddle-wheel diruthenium complexes for asymmetric catalysis

Abstract

The development of robust and reactive chiral catalysts is a fundamental aim in asymmetric catalysis, and crucial for providing efficient methods for synthesizing chiral molecules. Chiral paddle-wheel bimetallic complexes provide a highly tunable chiral environment in rhodium-catalysed asymmetric carbene/nitrene transfer reactions and Lewis acid-catalysed reactions. Chiral paddle-wheel complexes having other transition metals as the reactive metal centre, however, have not yet been identified in asymmetric catalysis. Here, we report the synthesis, structures and high catalytic performances of chiral paddle-wheel diruthenium complexes. The cationic chiral diruthenium complex [Ru2((S)-BPTPI)4]+ exhibited remarkable reactivity as a Lewis acid catalyst for asymmetric hetero-Diels–Alder reactions, achieving a turnover number of up to 1,880,000 with high enantioselectivity (>90% e.e.). The chiral diruthenium complexes also exhibited good reactivity and high enantioselectivity in C–H amination and cyclopropanation reactions under oxidizing conditions, indicating their high tolerance towards oxidation. Our results reveal the chiral paddle-wheel diruthenium scaffold as a promising platform for asymmetric catalysis.

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Fig. 1: Asymmetric catalysis using chiral paddle-wheel bimetallic complexes.
Fig. 2: Synthesis and structures of chiral paddle-wheel diruthenium complexes.
Fig. 3: Catalytic asymmetric HDA reactions with low catalyst loading.
Fig. 4: Catalytic asymmetric reactions using chiral diruthenium complexes under oxidizing conditions.
Fig. 5: Cyclic voltammograms of the chiral dirhodium and diruthenium complexes.

Data availability

Experimental procedures and characterization data for the catalysts and the synthesized compounds are included in the Supplementary Information. Crystallographic data are available from the Cambridge Crystallographic Data Centre with the following codes: 1-ClO4 (CCDC 1982959), 2-Cl (CCDC 1983066), [Rh2((S)-BPTPI)4] (CCDC 1982958) and 7d (CCDC 1982956). Other data are available from the corresponding authors upon request.

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Acknowledgements

This work was supported in part by JSPS KAKENHI Grant Numbers JP15H05802 (S.M.) and JP15H05804 (T.H.) in Precisely Designed Catalysts with Customized Scaffolding, and JSPS KAKENHI Grant Numbers JP18H04637 (T.Y.) and JP18H04651 (A.O.) in Hybrid Catalysis. We thank M. Kondo and S. Masaoka of Osaka University and T. Enomoto of the University of Tokyo for their support in the electrochemical analysis.

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Contributions

T.M., T.S., Y. Kumagai, K.T., Y. Kamei and F.K. synthesized the chiral diruthenium complexes. T.M., T.S., T.K. and T.Y. analysed the X-ray structures of the diruthenium and dirhodium complexes. S.K., A.O. and T.H. contributed to the EPR analysis of the diruthenium complexes. T.Y. performed EPR simulations. T.M. (C–H amination reactions), Y. Kumagai (HDA reactions) and K.T. (cyclopropanation reactions) mainly performed and analysed the catalytic asymmetric reactions and characterized the products. T.M. and M.K. performed and analysed the cyclic voltammetry experiments. T.M., T.S., M.A., M.K., T.Y. and S.M. conceived and designed the experiments, and prepared the manuscript. All authors contributed to discussions and commented on the manuscript.

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Correspondence to Tatsuhiko Yoshino or Shigeki Matsunaga.

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Supplementary information

Supplementary Information

Supplementary methods, Figs. 1–19, Tables 1–8, Notes 1 and 2, references and copies of NMR and HPLC charts.

Supplementary Data 1

Cif file for 7d.

Supplementary Data 2

Cif file for Rh2((S)-BPTPI)4.

Supplementary Data 3

Cif file for 1-ClO4.

Supplementary Data 4

Cif file for 2-Cl.

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Miyazawa, T., Suzuki, T., Kumagai, Y. et al. Chiral paddle-wheel diruthenium complexes for asymmetric catalysis. Nat Catal 3, 851–858 (2020). https://doi.org/10.1038/s41929-020-00513-w

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