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Enantiodivergent epoxidation of alkenes with a photoswitchable phosphate manganese-salen complex

Nature Synthesis volume 1, pages 873–882 (2022)Cite this article

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Abstract

The development of enantiodivergent catalysts capable of preparing both enantiomeric products from one substrate in a controlled fashion is challenging. Introducing a switching function into the catalyst can address this challenge, allowing the chiral reaction environment to reversibly change during catalysis. Here we report a photoswitchable phosphate ligand, derived from 2,2′-biphenol, which axially coordinates as the counterion to an achiral manganese(III)-salen catalyst, providing the latter with the ability to switch stereoselectivity in the epoxidation of alkenes. The enantiomers of the chiral ligand exist as a pair of pseudo-enantiomers, which can be interconverted by irradiation with light of different wavelengths. The opposite axial chirality of these pseudo-enantiomers is efficiently transferred to the manganese(III)-salen catalyst. With this switchable supramolecular catalyst, the enantioselectivity of the epoxidation of a variety of alkenes can be controlled, resulting in opposite enantiomeric excesses of the epoxide products. This transfer of chirality from a photoswitchable anionic ligand to a metal complex broadens the scope of supramolecular catalysts.

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Fig. 1: Structures of compounds.
Fig. 2: Synthesis and resolution of photoswitchable manganese(III)-salen catalyst Mn2.
Fig. 3: Ultraviolet–visible and CD spectroscopic studies of the photochemical switching of (S,M,Ra)-1 and (S,M,Ra)-Mn2.
Fig. 4: NMR spectroscopy study of the photochemical switching of Rac-1.
Fig. 5: X-ray crystal structures of the stable and metastable forms of Mn2.
Fig. 6: Enantioselective epoxidations.

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Data availability

The authors declare that the data supporting the findings of this study are included in the paper and the Supplementary Information file. Any further relevant data are available from the corresponding authors on request. Crystallographic data for the structure Rac-Mn2 reported in this article have been deposited at the Cambridge Crystallographic Data Centre (CCDC), under deposition number 2125340. Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/.

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Acknowledgements

This work was financially supported by the European Research Council (ERC Advanced Grant Number 74092 to R.J.M.N. and ERC Advanced Grant Number 227897 to B.L.F.) and by the Dutch Ministry of Education, Culture, and Science (Gravitation Programme 024.001.035).

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Author notes

  1. These authors contributed equally: Xiaofei Chen, Pieter J. Gilissen.

Authors and Affiliations

  1. Institute for Molecules and Materials, Radboud University, Nijmegen, The Netherlands

    Xiaofei Chen, Pieter J. Gilissen, Paul Tinnemans, Floris P. J. T. Rutjes, Johannes A. A. W. Elemans & Roeland J. M. Nolte

  2. Aix-Marseille Université, CNRS, Centrale Marseille, iSm2, Marseille, France

    Nicolas Vanthuyne

  3. Stratingh Institute for Chemistry, University of Groningen, Groningen, The Netherlands

    Ben L. Feringa

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Contributions

R.J.M.N. conceived the project. P.J.G. and F.P.J.T.R. designed the synthesis of compound 1. P.J.G. carried out the synthesis of 1 and investigated the photochemical properties of compounds 1 and Mn2. X.C. performed the catalysis experiments and grew the crystals. P.T. determined and analysed the crystal structure. N.V. separated the enantiomers of 1 by chiral HPLC. B.L.F contributed with his knowledge on molecular photoswitches. R.J.M.N. and J.A.A.W.E. supervised the project. All authors discussed the results and helped write and discuss the manuscript.

Corresponding authors

Correspondence to Ben L. Feringa, Johannes A. A. W. Elemans or Roeland J. M. Nolte.

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Peer review information

Nature Synthesis thanks Zoraida Freixa and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary handling editor: Peter Seavill, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–90, Discussion and Tables 1–8.

Supplementary Data 1

Crystallographic data for Compound Rac-Mn2, CCDC 2125340.

Source data

Source Data Fig. 3

Unprocessed UV-vis and ECD data.

Source Data Fig. 4

Unprocessed 1H NMR data.

Source Data Fig. 6

Unprocessed chiral HPLC data.

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Chen, X., Gilissen, P.J., Tinnemans, P. et al. Enantiodivergent epoxidation of alkenes with a photoswitchable phosphate manganese-salen complex. Nat. Synth 1, 873–882 (2022). https://doi.org/10.1038/s44160-022-00157-7

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