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Asymmetric construction of tetrahedral chiral zinc with high configurational stability and catalytic activity

Author

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  • Kenichi Endo

    (Graduate School of Science, The University of Tokyo
    Institute for Chemical Research, Kyoto University, Gokasho)

  • Yuanfei Liu

    (Graduate School of Science, The University of Tokyo)

  • Hitoshi Ube

    (Graduate School of Science, The University of Tokyo)

  • Koichi Nagata

    (Graduate School of Science, The University of Tokyo
    Graduate School of Science, Tohoku University, Aoba-ku)

  • Mitsuhiko Shionoya

    (Graduate School of Science, The University of Tokyo)

Abstract

Chiral metal complexes show promise as asymmetric catalysts and optical materials. Chiral-at-metal complexes composed of achiral ligands have expanded the versatility and applicability of chiral metal complexes, especially for octahedral and half-sandwich complexes. However, Werner-type tetrahedral complexes with a stereogenic metal centre are rarely used as chiral-at-metal complexes because they are too labile to ensure the absolute configuration of the metal centre. Here we report the asymmetric construction of a tetrahedral chiral-at-zinc complex with high configurational stability, using an unsymmetric tridentate ligand. Coordination/substitution of a chiral auxiliary ligand on zinc followed by crystallisation yields an enantiopure chiral-only-at-zinc complex (> 99% ee). The enantiomer excess remains very high at 99% ee even after heating at 70 °C in benzene for one week. With this configurationally stable zinc complex of the tridentate ligand, the remaining one labile site on the zinc can be used for a highly selective asymmetric oxa-Diels-Alder reaction (98% yield, 87% ee) without substantial racemisation.

Suggested Citation

  • Kenichi Endo & Yuanfei Liu & Hitoshi Ube & Koichi Nagata & Mitsuhiko Shionoya, 2020. "Asymmetric construction of tetrahedral chiral zinc with high configurational stability and catalytic activity," Nature Communications, Nature, vol. 11(1), pages 1-7, December.
    • Handle: RePEc:nat:natcom:v:11:y:2020:i:1:d:10.1038_s41467-020-20074-7
    DOI: 10.1038/s41467-020-20074-7
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