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Preparation of chiral-at-metal catalysts and their use in asymmetric photoredox chemistry

Nature Protocols volume 13, pages 605632 (2018) | Download Citation

Abstract

Asymmetric catalysis is a powerful approach for the synthesis of optically active compounds, and visible light constitutes an abundant source of energy to enable chemical transformations, which are often triggered by photoinduced electron transfer (photoredox chemistry). Recently, bis-cyclometalated iridium(III) and rhodium(III) complexes were introduced as a novel class of catalysts for combining asymmetric catalysis with visible-light-induced photoredox chemistry. These catalysts are attractive because of their unusual feature of chirality originating exclusively from a stereogenic metal center, which offers the prospect of an especially effective asymmetric induction upon direct coordination of the substrate to the metal center. As these chiral catalysts contain only achiral ligands, special strategies are required for their synthesis. In this protocol, we describe strategies for preparing two types of chiral-at-metal catalysts, namely the Λ- and Δ-enantiomers (left- and right-handed propellers, respectively) of the iridium complex IrS and the rhodium complex RhS. Both contain two cyclometalating 5-tert-butyl-2-phenylbenzothiazoles in addition to two acetonitrile ligands and a hexafluorophosphate counterion. The two cyclometalated ligands set the propeller-shaped chiral geometry, but the acetonitriles are labile and can be replaced by substrate molecules. The synthesis protocol consists of three stages: first, preparation of the ligand 5-tert-butyl-2-phenylbenzothiazole; second, preparation of salicylthiazoline (used for iridium) and salicyloxazoline (used for rhodium) chiral auxiliaries; and third, the auxiliary-mediated synthesis of the individual enantiopure Λ- and Δ-configured catalysts. This class of stereogenic-only-at-metal complexes is of substantial value in the field of asymmetric catalysis, offering stereocontrolled radical reactions based on visible-light-activated photoredox chemistry. Representative examples of visible-light-induced asymmetric catalysis are provided.

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Acknowledgements

Funding from the Deutsche Forschungsgemeinschaft (ME 1805/13-1) is gratefully acknowledged. We are grateful for careful revisions of Boxes 1 and 2 by H. Huo.

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Author notes

    • Jiajia Ma
    •  & Xiao Zhang

    These authors contributed equally to this work.

Affiliations

  1. Fachbereich Chemie, Philipps-Universität Marburg, Marburg, Germany.

    • Jiajia Ma
    • , Xiao Zhang
    • , Xiaoqiang Huang
    • , Shipeng Luo
    •  & Eric Meggers

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Contributions

E.M. coordinated the project. J.M., X.Z., X.H., and S.L. performed the syntheses. E.M., J.M., and X.Z. wrote the manuscript. J.M. and X.Z. contributed equally to this work.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Eric Meggers.

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https://doi.org/10.1038/nprot.2017.138

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