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

Kenichi Endo, Yuanfei Liu, Hitoshi Ube, Koichi Nagata and Mitsuhiko Shionoya ()
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Kenichi Endo: Graduate School of Science, The University of Tokyo
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
Mitsuhiko Shionoya: Graduate School of Science, The University of Tokyo

Nature Communications, 2020, vol. 11, issue 1, 1-7

Abstract: 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.

Date: 2020
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DOI: 10.1038/s41467-020-20074-7

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