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

Abstract

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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Fig. 1: Cp*Rh(iii) or CpxRh(iii)-catalysed asymmetric reactions.
Fig. 2: Preparation of [Cp*RhLN][(S)-BINSate] 2.
Fig. 3: Proposed catalytic cycle.

Change history

  • 03 January 2019

    In the version of this Article originally published, four important papers for transition metal/chiral anion asymmetric catalysis and 1,1'-binaphthyl-2,2'-disulfonate (BINSate) were erroneously omitted. These have now been added into the reference list at numbers 33, 43, 57 and 58, and the list renumbered accordingly:

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Acknowledgements

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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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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Correspondence to Tatsuhiko Yoshino or Shigeki Matsunaga.

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Supplementary Methods, Supplementary Figures 1–64, Supplementary References

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Satake, S., Kurihara, T., Nishikawa, K. et al. Pentamethylcyclopentadienyl rhodium(III)–chiral disulfonate hybrid catalysis for enantioselective C–H bond functionalization. Nat Catal 1, 585–591 (2018). https://doi.org/10.1038/s41929-018-0106-5

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