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Pentamethylcyclopentadienyl rhodium(III)–chiral disulfonate hybrid catalysis for enantioselective C–H bond functionalization

Nature Catalysisvolume 1pages585591 (2018) | Download Citation


Though Cp*Rh(iii) complexes are prominent and versatile catalysts for C–H bond functionalization reactions, catalytic stereocontrol is difficult due to the lack of vacant coordination sites. Here, we report a hybrid strategy for inducing chirality without using previously reported chiral Cpx ligands. A preformed hybrid catalyst, [Cp*RhLN][6,6′-Br-(S)-BINSate], catalysed C–H activation and subsequent conjugate addition of 2-phenylpyridine derivatives to enones in good yield and enantioselectivity (enantiomeric ratio up to 95:5). In addition to 2-phenylpyridines, the conjugate addition of 6-arylpurines proceeded with an enantiomeric ratio of up to 91:9 using [Cp*RhLN][(R)-SPISate]. The results demonstrate that a chiral organic anion can efficiently control the enantioselectivity of Cp*Rh(iii)-catalysed C–H bond functionalization without a chiral Cpx ligand.

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This work was supported in part by JST ACT-C grant number JPMJCR12Z6, Japan, JSPS KAKENHI grant numbers JP15H05802 and JP15H05810 in Precisely Designed Catalysts with Customized Scaffolding, JSPS KAKENHI grant number JP18H04637 in Hybrid Catalysis, JSPS KAKENHI grant number JP17K15417, and The Asahi Glass Foundation and Astellas Foundation (to S.M.). We thank J. Hasegawa at Hokkaido University for fruitful discussion on the reaction mechanism.

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  1. Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo, Japan

    • Shun Satake
    • , Takumaru Kurihara
    • , Tatsuhiko Yoshino
    •  & Shigeki Matsunaga
  2. Graduate School of Engineering, Nagoya University, Nagoya, Japan

    • Keisuke Nishikawa
    • , Takuya Mochizuki
    • , Manabu Hatano
    •  & Kazuaki Ishihara


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S.S., T.K., K.N., T.M. and T.Y. performed the experiments and analysed the data. S.S., M.H., K.I., 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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The authors declare no competing interests.

Corresponding authors

Correspondence to Tatsuhiko Yoshino or Shigeki Matsunaga.

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    Supplementary Methods, Supplementary Figures 1–64, Supplementary References

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