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Organosodium compounds for catalytic cross-coupling

Nature Catalysis volume 2, pages 297–303 (2019)Cite this article

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Abstract

Sodium is the most abundant alkali metal in the Earth’s crust and the ocean. However, organosodium compounds have long been considered inferior to organolithium compounds, which have instead dominated synthetic organic chemistry during the last century. Despite being largely neglected because of their reactive nature, it is worth re-exploring organosodium chemistry, in light of the growing demand for sustainable syntheses without recourse to less abundant elements such as lithium. Herein, we demonstrate that, contrary to common belief, organosodium compounds can be easily prepared from aryl chlorides or (hetero)arenes and easy-to-handle sodium dispersion and, after being transmetallated to the corresponding zinc and boron compounds, they readily participate in the Negishi and Suzuki–Miyaura cross-coupling reactions, fundamental carbon–carbon bond-forming reactions in organic synthesis. Direct coupling reactions with organosodium species were also possible.

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Fig. 1: Preparation of organometallic compounds and the subsequent cross-coupling reactions.
Fig. 2: Preparation of arylsodiums from aryl chlorides and sodium dispersion.
Fig. 3: Palladium-catalysed Negishi cross-coupling reactions using arylsodiums.
Fig. 4: Palladium-catalysed Suzuki–Miyaura cross-coupling reactions using arylsodiums.
Fig. 5: Palladium-catalysed direct cross-coupling reactions using arylsodiums.

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The data that support the findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

The authors thank Okayama University and KOBELCO ECO-Solutions Co., Ltd for financial support.

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Authors and Affiliations

  1. Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University, Kita-ku, Okayama, Japan

    Sobi Asako, Hirotaka Nakajima & Kazuhiko Takai

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  1. Sobi Asako
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  2. Hirotaka Nakajima
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  3. Kazuhiko Takai
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Contributions

S.A. and K.T. conceived and designed the experiments. H.N. performed the experiments. S.A. and K.T. prepared the manuscript. All authors contributed to discussions.

Corresponding authors

Correspondence to Sobi Asako or Kazuhiko Takai.

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Competing interests

S.A. and K.T. are listed as inventors on patent applications (JP2017/247538, JP2018/005719, JP2018/099899) that cover the cross-coupling reactions presented in this paper.

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Supplementary Methods, Supplementary Figures 1–4, Supplementary References

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Asako, S., Nakajima, H. & Takai, K. Organosodium compounds for catalytic cross-coupling. Nat Catal 2, 297–303 (2019). https://doi.org/10.1038/s41929-019-0250-6

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