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

Kenichi Endo, Yuanfei Liu, Hitoshi Ube, Koichi Nagata, Mitsuhiko Shionoya

Research output: Contribution to journalArticlepeer-review

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.

Original languageEnglish
Article number6263
JournalNature communications
Volume11
Issue number1
DOIs
Publication statusPublished - 2020 Dec

ASJC Scopus subject areas

  • Chemistry(all)
  • Biochemistry, Genetics and Molecular Biology(all)
  • Physics and Astronomy(all)

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