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Light-driven C–O coupling of carboxylic acids and alkyl halides over a Ni single-atom catalyst

Nature Synthesis volume 2, pages 1092–1103 (2023)Cite this article

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Abstract

Although visible-light-driven dual photoredox catalysis, a method that combines photoabsorbers and transition metals, has become a powerful tool to conduct coupling reactions, resource economical and scalability issues persist, owing to the use of catalysts and light absorbers that exploit critical raw materials (such as iridium complexes), and are homogeneous in nature. Here we report the merger of metallic single-atom and photoredox catalysis, in the form of a Ni atom-supported carbon nitride material, for the C–O coupling of carboxylic acids and alkyl halides. This operationally straightforward system, composed of only earth-abundant components, exhibits a wide functional group tolerance. Additionally, short reaction times, facile recovery and high catalyst stability make this method highly attractive for industrial applications.

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Fig. 1: Established and current catalytic work on the formation of C–O cross-coupled products.
Fig. 2: Catalyst characterization.
Fig. 3: Metallaphotocatalytic optimization, recyclability tests and system comparison studies.
Fig. 4: DFT-calculated metallaphotocatalytic C–O coupling cycle.

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Data availability

All the data supporting the findings of this study are available within the article and its supplementary information and also from the corresponding authors upon reasonable request.

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Acknowledgements

This work was supported by the European Commission through a Marie Skłodowska-Curie Fellowship (101031710, M.A.B.) and Horizon Europe fund for societal challenges (101057430, G.V.), by the Italian Ministry of Education, University and Research (MIUR) through the PRIN Project 20179337R7 (G.D.L., S.T. and G.P.), and by the COST (European Cooperation in Science and Technology) Action 18234 (G.D.L., S.T. and G.P.). E. Vittorio Pasini, P. Piscioneri and C. Basano, from Politecnico di Milano, are greatly thanked for help during catalytic experiments. The authors acknowledge S. Agnoli from the University of Padua (XPS studies), G. Divitini from the Italian Institute of Technology (HRTEM analyses) and J. Liu at the Dalian University of Technology for their respective input on the paper. L.M. thanks E. Borfecchia from Università di Torino for useful discussion about the XAS data.

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Authors and Affiliations

  1. Department of Chemistry, Materials, and Chemical Engineering ‘Giulio Natta’, Politecnico di Milano, Milan, Italy

    Mark A. Bajada, Vincenzo Ruta, Alessandra Sivo & Gianvito Vilé

  2. Department of Materials Science, Università di Milano Bicocca, Milan, Italy

    Giovanni Di Liberto, Sergio Tosoni & Gianfranco Pacchioni

  3. Department of Chemistry and Interdepartmental Centre NIS, Università di Torino, Turin, Italy

    Lorenzo Mino & Nicolò Allasia

Authors
  1. Mark A. Bajada
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Contributions

G.V. and M.A.B. conceived the project and devised the experiments. M.A.B. synthesized and characterized the catalysts. M.A.B. and V.R. conducted the metallaphotocatalytic tests and analysed the data, with assistance from A.S. V.R. purified, isolated, and characterized all compounds in the substrate scope. G.D.L., S.T., and G.P. performed DFT calculations. L.M. assisted during analysis of the X-ray spectra, while N.A. and L.M. conducted IR experiments and analysed the data. M.A.B. and G.V. wrote the paper with contributions and discussions from all co-authors.

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Correspondence to Sergio Tosoni or Gianvito Vilé.

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Supplementary information

Supplementary Information

Supplementary Materials and methods and experimental details, Table 1 and Figs. 1–9.

Source data

Source Data Fig. 2

XANES and EXAFS data used to compile the spectra portrayed in Fig. 2a,b.

Source Data Fig. 3

Processed catalytic data for system optimization, recyclability test and alternative catalyst screening.

Source Data Fig. 4

Zip folder enclosing a .txt file reporting the relative energies of all structures displayed in the reaction cycle and .cif files for all the computed structures.

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Bajada, M.A., Di Liberto, G., Tosoni, S. et al. Light-driven C–O coupling of carboxylic acids and alkyl halides over a Ni single-atom catalyst. Nat. Synth 2, 1092–1103 (2023). https://doi.org/10.1038/s44160-023-00341-3

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